Process for the ruthenium catalyzed trans-selective hydrostannation of alkynes

ABSTRACT

The present invention refers to a process for the ruthenium-catalyzed trans-selective hydrostannation of alkynes and the so-obtained products. The inventive process makes use of a tin hydride which is reacted with an alkyne in the presence of a cyclopentadienyl-coordinated ruthenium catalyst.

This application is a 371 of PCT/EP2014/072068, filed Oct. 14, 2014,which claims foreign priority benefit under 35 U.S.C. §119 of theEuropean Patent Application No. 13189792.8 filed Oct. 22, 2013, thedisclosures of which are incorporated herein by reference.

The present invention refers to a process for the ruthenium catalyzedtrans-selective hydrostannation of alkynes and the so-obtained products.

The hydrostannation of alkynes is an indispensable method for thesynthesis of alkenyltin reagents (alkenylstannanes) that find extensiveuse in preparative chemistry (M. Pereyre, J. P. Quintard, A. Rahm, Tinin Organic Synthesis, Butterworth, London, 1987; A. Orita, J. Otera, in:Main Group Metals in Organic Synthesis (H. Yamamoto, K. Oshima, Eds.),Wiley-VCH, Weinheim, 2004, Vol. 2, p. 621). The Stille cross couplingreaction is arguably the most important application of organotinreagents in general and alkenyltin reagents in particular (V. Farina, V.Krishnamurthy, W. J. Scott, Org. React. 1997, 50, 1). Other importantapplications of alkenyltin reagents involve, but are not limited to,metal-for-tin exchange, in particular lithium-for-tin exchange, as wellas halogen-for-tin exchange reactions.

Tin hydrides can be added to alkynes under conditions involving theformation of free radicals as the reactive intermediates. To this end,the addition reactions are usually carried out at elevated temperaturesin the presence of radical initiators such as azoisobutyronitrile (AIBN)or under ultrasonication. Under such conditions, alkynes usually affordE/Z-mixtures of the corresponding alkenylstannanes (J. A. Marshall in:Organometallics in Synthesis (M. Schlosser, Ed.), Wiley, Chichester,2002, 2^(nd) Ed., p. 353). The product ratio can change with time as thetin radicals involved in the reactions can lead to secondaryisomerization of the kinetic products initially formed. Radicalhydrostannation reactions are usually not applicable to substrates thatcontain other sites of unsaturation (alkenes, allenes) in addition tothe alkyne, or that contain other functional groups that will react withintermediate tin radicals (halides, azides, thioethers, thiocarbamatesetc).

Alternatively, tin hydrides can be added to alkynes in the presence ofmetal catalysts (N. D. Smith, J. Mancuso, M. Lautens, Chem. Rev. 2000,100, 3257). A large variety of different transition metal catalysts hasbeen investigated, with palladium, nickel, rhodium and molybdenum beingmost commonly used. Largely independent of the chosen transition metalcatalyst and as a consequence of the proposed reaction mechanism, suchadditions usually occur by suprafacial delivery of hydrogen and tin tothe same π-face of a given starting material (cis-addition mode), thusfurnishing the E-isomer of the resulting alkenylstannane. Although theexact mechanisms of such reactions are not always clear, catalyticcycles based on oxidative addition of the catalyst into the Sn—H bond,hydrometalation of the alkyne substrate, followed by reductiveelimination are generally proposed.

Exceptions of this cis-addition mode in transition metal catalyzedhydrostannation reactions are rare and usually substrate dependent.Thus, certain acetylenes conjugated to strongly electron withdrawingketone group were shown to give products derived from formaltrans-addition under palladium catalysis, whereas the correspondingacetylenic esters react by the normal cis-addition mode under the samereaction conditions (J. C. Cochran et al., Tetrahedron Lett. 1990, 31,6621). It can therefore not be excluded that a secondary isomerizationprocess might account for the unusual stereochemical outcome in theketone series. Likewise, terminal alkynes were found to produce productmixtures containing varying amounts of formal trans-addition products inthe presence of various transition metal catalysts (K. Kikukawa et al.,Chem. Lett. 1988, 881).

Highly selective formal trans-hydrostannations of terminal or internalalkynes have so far only been accomplished with the help of strong Lewisacid additives or catalysts (N. Asao et al., J. Org. Chem. 1996, 61,4568; V. Gevorgyan et al., Chem. Commun. 1998, 37; M. S. Oderinde etal., Angew. Chem. 2012, 124, 9972). The best additives or catalystscurrently known are ZrCl₄, HfCl₄ and B(C₆F₅)₃, which are thought toabstract the hydride from the Bu₃SnH reagent with formation of atransient Bu₃Sn⁺ species that coordinates the alkyne. Hydride deliveryto the resulting complex occurs trans to the bulky R₃Sn-residue andhence results in formal trans-hydrostannation. Although thetrans-selectivity is usually excellent, the very high Lewis acidity ofthe additives or catalysts severely limits the compatibility of thismethod with functional groups; even a simple benzyl ether was reportedto quench the activity of ZrCl₄ and hence prevent thetrans-hydrostannation from occurring (N. Asao et al., J. Org. Chem.1996, 61, 4568). The very high Lewis acidity of the additives orcatalysts is also the reason why the reaction is best carried out inunfunctionalized hydrocarbon solvents such as toluene or hexane, inwhich ZrCl₄ as the preferred catalyst is not well soluble. The use ofTHF or CH₂Cl₂, which dissolve ZrCl₄ and certain substrates moreeffectively, were reported to giver lower stereoselectivities andchemical yields. Another disadvantage is the fact that thetrans-hydrostannation of internal alkynes requires stoichiometricamounts of ZrCl₄ for optimal results.

The inventors of the present invention found the first broadlyapplicable, functional group tolerant and highly stereoselectiveruthenium catalyzed trans-hydrostannation of alkynes. Previous rutheniumcatalyzed hydrostannations of terminal alkynes were shown to deliverproduct mixtures containing different regio- as well as stereoisomersthat are of little preparative use (K. Kikukawa et al., Chem. Lett.1988, 881). In contrast, the present invention is directed to a processfor highly stereoselective trans-hydrostannation of alkynes comprisingthe steps of reacting an alkyne of the formula I

with a tin hydride of the formula X¹X²X³SnH in the presence of aruthenium catalyst to yield an alkene of the general formula (II):

In the alkyne of the general formula (I) and in the alkene of thegeneral formula (II), respectively, R¹ and R² may be the same ordifferent and may each be selected from:

-   -   I. straight chain or branched chain aliphatic hydrocarbons,        preferably having 1 to 20 carbon atoms, or cyclic aliphatic        hydrocarbons, preferably having 3 to 20 carbon atoms, said        aliphatic hydrocarbons optionally including heteroatoms and/or        aromatic hydrocarbons and/or heteroaromatic hydrocarbons in the        chain and/or having one or more substituents selected from        C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic        hydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or        aryl-(C₁-C₆)-alkyl, heteroaryl-(C₁-C₆)-alkyl, or heteroatoms, or    -   II. aromatic hydrocarbons having 5 to 20 carbon atoms or        heteroaromatic hydrocarbons having 1 to 20 carbon atoms, said        aromatic or heteroaromatic hydrocarbons each optionally having        one or more substituents selected from C₁-C₂₀-alkyl,        C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic hydrocarbon, C₅ to        C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,        heteroaryl-(C₁-C₆)-alkyl, heteroatoms, or        one of R¹ and R² is selected from hydrogen, halogen,        —SiR*R**R***, wherein R*, R**, R*** can be the same or different        and may have the meaning as given under I. and II., and the        other of R¹ and R² has the meaning as given under I. or II.        or        R¹ and R² together form an aliphatic hydrocarbon chain having 6        to 30 carbon atoms, optionally including heteroatoms and/or        aromatic hydrocarbons in the chain and/or optionally having one        or more substituents selected from C₁-C₂₀-alkyl,        C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic hydrocarbon, C₅ to        C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,        heteroaryl-(C₁-C₆)-alkyl, said aliphatic hydrocarbon chain        optionally being substituted by one or more substituents        selected from heterosubstituents, straight chain, branched        chain, cyclic aliphatic C₁ to C₂₀ hydrocarbons, C₆ to C₂₀        aromatic hydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon,        aryl-(C₁-C₆)-alkyl, or heteroaryl-(C₁-C₆)-alkyl or heteroatoms.

Preferably, R¹ and R² may be the same or different and may each beselected from straight chain or branched chain aliphatic hydrocarbonshaving 1 to 20 carbon atoms optionally including heteroatoms and/oraromatic hydrocarbons in the chain or aromatic hydrocarbons having 5 to20 carbon atoms, optionally having one or more substituents selectedfrom C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatichydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, or heteroatoms, or

R¹ and R² together form an aliphatic hydrocarbon chain structure having8 to 20 carbon atoms, optionally including heteroatoms and/or aromatichydrocarbons in the chain and/or optionally having one or moresubstituents selected from C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ toC₂₀ aromatic hydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon oraryl-(C₁-C₆)-alkyl, heteroaryl-(C₁-C₆)-alkyl, said chain structureoptionally being substituted by one or more substituents selected fromheterosubstituents, straight chain, branched chain, cyclic aliphatic C₁to C₂₀ hydrocarbons, C₆ to C₂₀ aromatic hydrocarbon, C₅ to C₂₀heteroaromatic hydrocarbon, aryl-(C₁-C₆)-alkyl, orheteroaryl-(C₁-C₆)-alkyl, orone of R¹ and R² is selected from hydrogen, halogen, —SiR*R**R***,wherein R*, R**, R*** can be the same or different and may each beselected from straight chain or branched chain aliphatic hydrocarbonshaving 1 to 20 carbon atoms optionally including heteroatoms and/oraromatic hydrocarbons in the chain or aromatic hydrocarbons having 5 to20 carbon atoms, optionally having one or more substituents selectedfrom C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatichydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, or heteroatoms.

R¹ and R² should preferably have a lower affinity to the Ru-central atomin the ruthenium complex than the alkyne moiety in order to avoidblocking of the reactive site thereof.

The substituents X¹, X² and X³ in the tin hydride of the formulaX¹X²X³SnH may be the same or different and may each be selected fromhydrogen, straight chain, branched chain or cyclic aliphatichydrocarbons, preferably having 1 to 20, preferably 1 to 16 carbonatoms, or aromatic hydrocarbons preferably having 6 to 22, preferably 6to 14 carbon atoms, or two of X¹ X² and X³ together form an aliphatichydrocarbon chain having 2 to 20 carbon atoms, preferably 2 to 10 carbonatoms in the chain, including said aliphatic hydrocarbons being bound toSn via oxygen (such as alkoxy), said aliphatic hydrocarbon groupoptionally including heteroatoms in the chain and/or optionally havingone or more substituents selected from C₁-C₂₀-alkyl,C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic hydrocarbon, C₁ to C₂₀heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, having identical or different alkyl groupswith 2 to 12 carbon atoms, halogen or heteroatoms wherein at least twoof X¹, X² and X³ are not hydrogen In said formula, X¹X²X³SnH, anyhydrogen directly bond to the Sn atom may also be deuterium.

Preferably, the tin hydride of the formula X¹X²X³SnH is represented bythe formula in which X¹, X² and X³ may be the same or different and mayeach be selected from straight chain, branched chain or cyclic C₁ to C₁₀aliphatic hydrocarbons each optionally being substituted by methyl,ethyl, propyl, butyl or isomers thereof, or one or more fluorine atoms.Examples of preferred tin hydrides are (lower alkyl)₃SnH or (loweralkyl)₂SnH₂ including partially or fully halogenated lower alkyl, suchas Me₃SnH, Bu₃SnH, Bu₂SnH₂, Cy₃SnH (Cy=cyclohexyl), (octyl)₃SnH,[CF₃(CF₂)₅(CH₂)₂]₃SnH, [CF₃(CF₂)₃(CH₂)₂]₃SnH.

In another embodiment of the current invention, the higher isotopomersof the tin hydride reagents of the general formula X¹X²X³SnH are used,in particular the corresponding tin deuterides of the general formulaX¹X²X³SnD, wherein the substituents X¹, X² and X³ can be chosen asdefined above.

The catalyst used in the inventive process is acyclopentadienyl-coordinated ruthenium complex containing the followingsubstructure:

wherein R_(cp1) to R_(cp5) may be the same or different and may each beselected from hydrogen or from straight chain, branched chain or cyclicaliphatic hydrocarbons, preferably having 1 to 20 carbon atoms,optionally including heteroatoms and/or aromatic hydrocarbons in thechain and/or optionally having one or more substituents selected fromC₁-C₂₀-alkyl, heterocycloalkyl, C₆ to C₂₀ aromatic hydrocarbon, C₅ toC₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl or heteroatoms and wherein further ligands arecoordinated to the central atom ruthenium.

Preferred are catalysts [Cp*RuL₃]X wherein Cp*=η⁵-C₅R_(5cp) with eachR_(cp) being H or preferably CH₃, and L being the same or differentligand/substituent and being selected from two electron-donatingligands/substituents such as CH₃CN, cycloalkadiene having 8 to 12 carbonatoms, or a catalyst complex of the formula [Cp*RuY_(n)] whereinCp*=η⁵-C₆R_(5cp) with each R_(cp) being H or preferably CH₃, and Y is ananionic ligand and being selected from hydrogen, halogen and n=2, 3, ora dimer or oligomer of the formula [Cp*RuY₂]_(n) wherein Cp*=η⁵-C₅R₅with R being H or CH₃ and Y is an anionic ligand and being selected fromhydrogen, halogen and n≧2. A preferred Ru-complex can be a cationiccomplex with an anionic counter ion X that is weakly coordinating, suchas PF₆ ⁻, SbF₆ ⁻, BF₄ ⁻, ClO₄ ⁻, F₃CCOO⁻, Tf₂N⁻,(Tf=trifluoromethanesulfonyl), TfO⁻, tosyl, [B[3,5-(CF₃)₂C₆H₃]₄]⁻,B(C₆F₅)₄ ⁻), Al(OC(CF₃)₃)₄ ⁻

The solvent used in the inventive process should be a low donor solventand may be selected from aliphatic, cycloaliphatic solvents, fluorinatedhydrocarbons, esters, ethers, ketones or mixtures thereof which may besubstituted by one or more heteroatoms such as pentane, hexane, CHCl₃,CH₂Cl₂, 1,2-dichloroethane, CH₃CN, ethyl acetate, acetone, THF, diethylether or methyl tert-butyl ether, 1,2-dimethoxyethane (glyme),bis(2-methoxyethyl)ether (diglyme), benzotrifluoride, as long as theyare not detrimental to the catalysed reaction. If the alkyne of theformula (I) itself is a liquid or in a liquid state, there might be noneed for a separate solvent. The catalyst is generally used in a molarratio of 0.1 to 10 mol-%, preferably 1 to 5 mol-% referred to the alkyneof the general formula (I).

The inventive process can be carried out in a temperature range from−78° C. to 100° C., preferably at ambient temperature of between 0° and30° C., and it proceeds at normal pressure already. If needed, thereaction can be carried out in a protective atmosphere such as nitrogenor argon.

A heterosubstituent as defined according to the invention can beselected from —O—, ═O, F, Cl, Br, I, CN, NO₂, a monohalogenomethylgroup, a dihalogenomethyl group, a trihalogenomethyl group, CF(CF₃)₂,SF₅, amine bound through N atom, —O-alkyl (alkoxy), —O-aryl, —O—SiR^(S)₃, S—R^(S), S(O)—R^(S), S(O)₂—R^(S), CO₂—R^(S), amide, bound through Cor N atom, formyl group, C(O)—R^(S). R^(S) ₃ may be, independently fromeach other, the same or different and may be each an aliphatic,heteroaliphatic, aromatic or heteroaromatic group, each optionally beingfurther substituted by one or more heterosubstituents, aliphatic,heteroaliphatic, aromatic or heteroaromatic groups. Preferably, theheterosubstituent is selected from ═O, F, Cl, Br, I, CN, NO₂, amonohalogenomethyl group, a dihalogenomethyl group, a trihalogenomethylgroup, CF(CF₃)₂, SF₅, amine bound through N atom, —O-alkyl (alkoxy),—O-aryl.

In more detail, C₁-C₂₀-alkyl can be straight chain or branched and has1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20carbon atoms. Alkyl might be lower alkyl such as C₁-C₅-alkyl, inparticular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butylor tert-butyl, likewise pentyl, 1-, 2- or 3-methylpropyl, 1,1-, 1,2- or2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-, 2, 3- or 4-methylpentyl,1,1-, 1,2-, 1,3-, 2,2-, 2,3- or 3,3-dimethylbutyl, 1- or 2-ethylbutyl,1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1,1,2- or1,2,2-trimethylpropyl. Substituted alkyl groups are trifluoromethyl,pentafluoroethyl and 1,1,1-trifluoroethyl.

Cycloalkyl might preferably be C₃-C₁₀-alkyl and may be cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

Alkenyl might be C₂-C₂₀ alkenyl. Alkynyl might be C₂-C₂₀ alkynyl.

Halogen is F, Cl, Br or I.

Alkoxy is preferably C₂-C₁₀ alkoxy such as methoxy, ethoxy, propoxy,iso-propoxy, tert-butoxy etc.

Heterocycloalkyl having one or more heteroatoms selected from among N, Oand S is preferably 2,3-dihydro-2-, -3-, -4- or -5-furyl,2,5-dihydro-2-, -3-, -4- or -5-furyl, tetrahydro-2- or -3-furyl,1,3-dioxolan-4-yl, tetrahydro-2- or -3-thienyl, 2,3-dihydro-1-, -2-,-3-, -4- or -5-pyrrolyl, 2,5-dihydro-1-, -2-, -3-, -4- or -5-pyrrolyl,1-, 2- or 3-pyrrolidinyl, tetrahydro-1-, -2- or -4-imidazolyl,2,3-dihydro-1-, -2-, -3-, -4- or -5-pyrazolyl, tetrahydro-1-, -3- or-4-pyrazolyl, 1,4-dihydro-1-, -2-, -3- or -4-pyridyl,1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5- or -6-pyridyl, 1-, 2-, 3- or4-piperidinyl, 2-, 3- or 4-morpholinyl, tetrahydro-2-, -3- or-4-pyranyl, 1,4-dioxanyl, 1,3-dioxan-2-, -4- or -5-yl, hexahydro-1-, -3-or -4-pyridazinyl, hexahydro-1-, -2-, -4- or -5-pyrimidinyl, 1-, 2- or3-piperazinyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or-8-quinolyl, 1,2,3,4-tetrahydro-1-, -2-, -3-, -4-, -5-, -6-, -7- or-8-isoquinolyl, 2-, 3-, 5-, 6-, 7- or8-3,4-dihydro-2H-benzo-1,4-oxazinyl.

Optionally substituted means unsubstituted or monosubstituted,disubstituted, trisubstituted, tetrasubstituted, pentasubstituted, oreven further substituted for each hydrogen on the hydrocarbon.

Including heteroatoms and/or aromatic hydrocarbons in the chain meansthat one or more carbon atoms in the chain might be replaced byheteroatoms such as N, O or S or part of an aromatic ring structure.

Aryl might be phenyl, naphthyl, biphenyl, anthracenyl, and otherpolycondensed aromatic systems.

Aryl-(C₁-C₆)-alkyl might be benzyl or substituted benzyl.

Heteroaryl having one or more heteroatoms selected from among N, O and Sis preferably 2- or 3-furyl, 2- or 3-thienyl, 1-, 2- or 3-pyrrolyl, 1-,2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-oxazolyl,3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl,2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, also preferably1,2,3-triazol-1-, -4- or -5-yl, 1,2,4-triazol-1-, -3- or -5-yl, 1- or5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl,1,3,4-thiadiazol-2- or -5-yl, 1,2,4-thiadiazol-3- or -5-yl,1,2,3-thiadiazol-4- or -5-yl, 3- or 4-pyridazinyl, pyrazinyl, 1-, 2-,3-, 4-, 5-, 6- or 7-Indolyl, 4- or 5-isoindolyl, 1-, 2-, 4- or5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6-or 7-benzoxazolyl, 3-, 4-, 5-, 6- or 7-benzisoxazolyl, 2-, 4-, 5-, 6- or7-benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 4-, 5-, 6- or7-benz-2,1,3-oxadiazolyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolyl, 1-, 3-,4-, 5-, 6-, 7- or 8-isoquinolyl, 3-, 4-, 5-, 6-, 7- or 8-cinnolinyl, 2-,4-, 5-, 6-, 7- or 8-quinazolinyl, 5- or 6-quinoxalinyl, 2-, 3-, 5-, 6-,7- or 8-2H-benzo-1,4-oxazinyl, also preferably 1,3-benzodioxol-5-yl,1,4-benzodioxan-6-yl, 2,1,3-benzothiadiazol-4- or -5-yl or 2,1,3-benzoxadiazol-5-yl.

The invention is further illustrated as follows:

The inventors have carried out an initial screening of catalysts andsolvents using tributyltin hydride as the reagent for thetrans-hydrostannation of alkynes. The results are indicated in thefollowing Table 1.

TABLE 1 Initial screening for the trans-hydrostannation usingcycloalkyne 1 as the substrate; for the sake of comparison, allreactions were stopped after only 15 min reaction time

3

4

5 X = Cl 6 X = H

Entry Solvent [Ru] Z:E Yield (%) 1 CH₂Cl₂ 3 86:14 96 2 dichloroethane 382:18 97 3 acetone 3 83:17 41 [a] 4 MeCN 3 82:18 66 5 Et₂O/CH₂Cl₂ (7:3)3 85:15 quant. [a] 6 diglyme 3 83:17 81 7 CH₂Cl₂ 4 63:37 83 8 CH₂Cl₂ 584:16 34 9 CH₂Cl₂ 7 89:11 85 10 CH₂Cl₂ 3 85:15 94 [b] 11 CH₂Cl₂ 3 86:1478 [c] [a] conversion rather than isolated yield; [b] the reaction wasperformed in the dark; [c] the reaction was performed in the presence of1 equivalent of TEMPO (2,2,6,6-tetramethyl-piperidin-1-oxyl; freeradical)

The reactions shown in Table 1 were carried out at 0.1 M concentrationin CH₂Cl₂ under argon; however, very similar results in terms of yieldand selectivity were obtained at different concentrations. The E:Zratios were determined by NMR and refer to the crude material prior towork up. Unless stated otherwise, the yields refer to analytically pureisolated material.

The inventors found that trans-selective hydrostannations proceed veryrapidly in the presence of [Cp*Ru(MeCN)₃]PF₆ (3) as one of the preferredcatalysts Thus, addition of 5 mol % of this complex to a solution of 1and Bu₃SnH in CH₂Cl₂ resulted in a very fast (<15 min), clean and highlytrans-selective hydrostannation (Z:E≧86:14, NMR) (entry 1). The productwas isolated in 96% yield The same excellent stereoselectivity wasrecorded when the hydrostannation was performed in the dark, whichexcludes that the major product Z-2 is formed by a secondaryphotochemical E→Z isomerization (entry 10). Likewise, the reactionproceeds with the same selectivity and in good yield when performed inthe presence of 1 equivalent of TEMPO, which is known to serve as anefficient radical trap (entry 11). This result demonstrates that theobserved trans-addition is not the result of a radical but of a truemetal-catalyzed process. Collectively, these data suggest that theobserved trans-addition is an inherent feature of the new methodology,and that the reaction is a true hydrostannation rather than anisomerization process.

A brief survey showed that the use of [Cp*Ru(MeCN)₃]PF₆ (3) in CH₂Cl₂ isa preferred catalyst. As evident from Table 1, several other solvents orsolvent mixtures gave similarly good stereoselectivities and good toexcellent yields. However, the use of toluene gave only low conversion.This result is thought to reflect the affinity of [LRu(MeCN)₃]⁺ (L=Cp,Cp*) towards arenes (and other conjugated π-systems), which leads to theformation of kinetically fairly stable adducts of type[Cp*Ru(η⁶-arene)]⁺. Other strong donor solvents also tend to give lowyields.

Formal replacement of the labile MeCN ligands on the cationic [Cp*Ru]⁺template by a kinetically more tightly bound cyclooctadiene (cod) moietyallows the reaction still to proceed but makes it less productive. Thus,the neutral variant [Cp*Ru(cod)Cl] (5) furnished no more than 34%conversion (GC) (entry 8). In this case, the tin reagent itself may helprelease a cationic species in solution by slow abstraction of thechloride from the ruthenium precatalyst. A similar process might accountfor the activation of the chloride-bridged complex 7 (entry 9). Althoughthe tested precatalysts greatly differ in efficiency, the E/Z-ratio wassimilarly high in all cases, which may indicate the formation of a(largely) common active species.

Of mechanistic significance is the observation of the inventors that theexquisite selectivity for trans-hydrostannation is somewhat compromisedupon formal replacement of the Cp* unit by the parent unsubstitutedcyclopentadienyl (Cp) ring present in [CpRu(MeCN)₃]PF₆ (4), although thetrans-addition product is still formed as the major compound (entry 7versus entry 1). Since this structural change hardly affects theelectronic properties of the ruthenium center, the stereodeterminingstep of the catalytic cycle likely has a large steric component. Apossible rationale is outlined below.

The optimal reaction conditions were applied to a set of representativealkyne derivatives to explore the scope and limitations of the newprocedure. As can be seen from the results compiled in Table 2, good tooutstanding selectivity for trans-hydrostannation was observed for avariety of substrates and the chemical yields were also good toexcellent. In close analogy to other hydrostannation reactions (N. D.Smith, J. Mancuso, M. Lautens, Chem. Rev. 2000, 100, 3257),unsymmetrical alkynes lead to the formation of regioisomers; careful NMRanalysis confirmed that either regioisomer derives from atrans-hydrostannation pathway. Ways to largely avoid such mixtures ofregioisomers are outlined below for alkyne substrates containing proticfunctionality.

As pointed out above, the current procedure is also applicable toterminal alkynes as well as to alkynes bearing a heteroelement directlybound to the triple bond; the heteroelements that can be directly boundto the triple bond include silicon and halogen, which are of particularpreparative relevance; in these cases, the resulting alkenyltinderivatives are usually formed with excellent regioselectivities.Likewise, it is important to recognize that the hydrostannation ofmethyl 5-hexynoate as a prototype terminal alkyne substrate led to thealkenylstannane as the largely major isomer, in which the tin residue isbound to the non-terminal carbon atom (Table 2, entry 21). In contrast,hydrostannation of methyl 5-hexynoate under free radical conditions haspreviously been reported to afford the regioisomeric alkenyltin compound(as a mixture of stereoisomers), in which the tin residue is at theterminal position (J. D. White et al., J. Am. Chem. Soc. 1995, 117,6224). This different outcome provides further evidence that the currentinvention is not a radical but a ruthenium-catalyzed process.

A variety of functional groups in the reaction system is tolerated,including ethers, esters, silyl ethers, sulfonates, ketones,phthalimides, azides, amides, Weinreb amides, carbamates, sulfonamides,alkenes, halides, a free carboxylic acid, unprotected hydroxyl groups aswell as different heterocycles. This functional group tolerance furthercorroborates that the observed trans-hydrostannation is not the resultof a radical process, since azides or halides are incompatible with tinradicals. Moreover, most of these functional group are not tolerated inthe literature-known trans-hydrostannation reactions effected bycatalytic or stoichiometric amounts of strong Lewis acids such as ZrCl₄,HfCl₄ and B(C₆F₅)₃ (N. Asao et al., J. Org. Chem. 1996, 61, 4568; V.Gevorgyan et al., Chem. Commun. 1998, 37; M. S. Oderinde et al., Angew.Chem. 2012, 124, 9972).

Further results of the inventors show that the formation of regioisomersin the trans-hydrostannation of unsymmetrical alkynes can be tuned bythe choice of the catalyst. A striking illustration is provided infollowing Scheme 1. Whereas the use of [Cp*Ru(MeCN)₃]PF₆ (3) gave a2.8:1 mixture, the isomer ratio was largely improved in favor of theα-isomer by the use of the oligomeric precursor [Cp*RuCl₂]_(n) (7) (n≧2)(prepared according to: N. Oshima et al., Chem. Lett. 1984, 1161). Thiseffect is preparatively highly useful and broadly applicable (seebelow).

Catalyst Combined yield α:β (NMR) [Cp*Ru(MeCN)₃]PF₆ (3) 91% 2.8:1[Cp*RuCl₂]_(n) (7) 88%  98:2

TABLE 2 Representative examples of alkenylstannanes prepared by theruthenium-catalyzed trans-hydrostannation reaction; in case wheremixtures of regioisomers are obtained, only the major regioisomer isdepicted and the reported Z:E ratio refers to this major regioisomer.Unless stated otherwise, all reactions were performed with Bu₃SnH inCH₂Cl₂ at ambient temperature using 5 mol % of [Cp*Ru(MeCN)₃]PF₆ as thecatalyst. Overall regioisomer Entry Major Product Yield [a] ratio Z:E 1

94% — >99:1   2

80% — 99:1 3

98% — 99:1 4

69% — >99:1   5

80% — 97:3 6

56% — 98:2 7

94% — 99:1 8

88% — 99:1 9

98% — >99:1   10

quant. — n.d. 11

97% — 95:5 12

82% 96:4 >99:1   13

98% 96:4 >99:1   14

94% 99:1 >99:1   15

90% 3.7:1  97:3 16

90% 1.9:1  >99:1   17

91% 2.8:1  >99:1   18

90% 1.5:1  99:1 19

77%  1:1 99:1 (α) 91-9 (β) 20

82% [b] 3.6:1  >99:1   21

73% [c] 97:3 [a] isolated yield of the product mixture, unless statedotherwise; [b] conversion (NMR) rather than isolated yield; [c] a CH₂Cl₂solution containing both, the alkyne substrate and Bu₃SnH, was slowlyadded to a solution of the catalyst in CH₂Cl₂; n.d. = not determined

The known affinity of [Cp*Ru] to arenes explains why tolane hardlyreacts under the above conditions, but modifying the reactionsconditions including testing different Ru-catalysts and tin hydridesshould enable the skilled man to find out suitable conditions. Theinventors assume that electron withdrawing substituents on the aromaticring might destabilize sandwich complexes of the general type[Cp*Ru(η⁶-arene)]⁺ (Gill, T. P. et al., Organometallics 1, 485-488(1982); Schmid, A. et al., Eur. J. Inorg. Chem. 2255-2263 (2003)). Infact, arylalkynes bearing electron withdrawing groups on the aromaticring reacted well, although they took longer to reach full conversion(see Table 2, entries 10, 16).

Although it is premature at this stage to draw a conclusive mechanisticpicture, the basic features of the trans-selective hydrostannation canbe rationalized as shown in Scheme 2.

The inventors assume that binding of an alkyne to the electrophilicmetal center of C subsequently favors coordination of the tin hydriderather than of a second alkyne on electronic grounds. In the resultingloaded complex E, the acetylene moiety is supposed to function as afour-electron donor, which explains why alkenes do not react under thechosen conditions. This bonding situation, in turn, facilitates aninner-sphere nucleophilic delivery of the hydride with formation of ametallacyclopropene F (η²-vinyl complex) without prior generation of adiscrete Ru—H species. It is very well precedented that the substituentsat the β-carbon atom of such complexes are configurationally labile andcan easily swap places via a η²→η¹→η² hapticity change (Frohnapfel, D.S. et al., Coord. Chem. Rev. 206-207, 199-235 (2000)). As they areapproximately orthogonal to the plane of the metallacyclopropene, thesheer size of the Cp* ring will exert a massive influence on thestereochemical outcome. As a consequence, isomer H, in which thehydrogen rather than the R group is oriented towards the bulky lid, willbe largely favored over F. This decisive steric factor loses weight ifthe lateral methyl groups of the Cp* ring are formally removed and[CpRu]-based catalysts are used. The trajectory of the ensuing reductiveelimination places the tin entity anti to the hydrogen atom and henceleads to the formation of an E-configured alkenylstannane product. It isemphasized, however, that it cannot be excluded that the order oftransfer of hydrogen and tin to the alkyne substrate could also bereversed, with the tin residue being delivered prior to delivery of thehydrogen atom.

It has been mentioned above that the proper choice of catalyst canimpart high levels of regioselectivity on the trans-hydrostannation ofunsymmetrical alkynes. This effect of matching substrate and catalyst isbroadly applicable. Further representative examples are shown in Table3. Excellent results are usually obtained when substrates containing anacidic or slightly acidic proton in proximity to the triple bond arereacted with the appropriate tin hydride in the presence of aCp*Ru-catalyst containing a chloride substituent. Preferred catalystsare [Cp*Ru(cod)Cl] (5), [Cp*RuCl₂]_(n) (7), or [(Cp*RuCl)₄] (8)(prepared according to: P. J. Fagan et al., Organometallics 1990, 9,1843). This strong directing effect might stem from a pre-orientation ofsubstrate and/or tin hydride within the coordination sphere of thecatalyst and/or from a change in mechanism.

This effect is particularly pronounced for propargylic alcohols,independent of whether their alcoholic function is primary, secondary ortertiary; increasing steric demand does not seem to override thispronounced bias, as is often the case in hydrostannations catalyzed byother transition metals. Comparison of Tab. 3, entries 7 and 8 confirmsthat the largely improved regioselectivity is intimately related withthe presence of an unprotected hydroxyl group and not merely caused bydipolar interactions in the transition state. Even if the —OH group islocated at a homopropargylic or bis-homopropargylic position,appreciable regioselectivity can be harnessed (Tab. 3, entries 12, 13,20, 21, 22).

Likewise, amides and sulfonamides at a propargylic (entry 14) orhomopropargylic position (entries 31-34) exert a strong directing effectin the presence of a chloride-containing ruthenium catalyst such as 7 or8. Tab. 3, entries 31-34 even suggest that the level of regioselectivityis directly correlated with the acidity of —NH group of the amide orsulfonamide. The example shown in entry 30 demonstrates that aheterocyclic ring containing a protic site is also able to exert astrong directing effect.

Moreover, the effect extends to acetylene carboxylate derivatives.Hydrostannations in the presence of the cationic catalyst 3, albeithighly trans-selective, were regio-indiscriminative (Tab. 2, entry 11and Tab. 3, entries 15, 17); in contrast, the use of complex 8 engendersa highly regioselective reaction at the proximal α-position of the acid(Tab. 3, entries 16, 19), whereas an acetylenic ester exhibits theopposite preference for stannylation at the distal β-site (entry 18).This dichotomy is obviously useful in preparative terms anddistinguishes the current method from other transition metal-catalyzedhydrostannations, which tend to be α-selective even in the acetylenicester series. It has been previously mentioned in this Patentapplication that the affinity of [Cp*Ru] to arenes, dienes, enynes orpolyenes likely explains why substrates containing such functionalitiesare less reactive or even unreactive under the conditions shown in Table2 of the current patent application. In contrast, several examplespresented in Table 3 suggest that a protic functionality in proximity toa triple bond—in combination with a chloride containing rutheniumcatalysts such as 5, 7 or 8—exerts a sufficiently strong activatingeffect (in addition to the effect on the regioselectivity oftrans-hydrostannation), thus allowing such otherwise poorly reactive oreven unreactive substrates to be trans-hydrostannylated with respectableto excellent yields and selectivities (Tab. 3, entries 25, 26, 27, 29).

This activating effect is also visible in the example shown in entry 35,in which a diyne substrate has been subjected to trans-hydrostannation.In this case, the triple bond next to the alcohol group reactspreferentially, while the distal triple bond remains largely unaffected.If one alkyne is terminal and another one is internal or silylated, eventhe cationic ruthenium complex [Cp*Ru(MeCN)₃]PF₆ (3) is capable ofimposing site-selectivity on diyne substrates: it is the terminal alkynewhich reacts with good to excellent selectivity. Representative examplesfor this ability to select amongst two alkynes are contained in theExperimental Section.

TABLE 3 trans-Hydrostannation of unsymmetrical alkynes containing proticfunctionalities in proximity to the triple bonds.^([a]) Yield EntryMajor Product Catalyst^([b]) α:β ^([c]) Z:E ^([c]) [%]  1  2  3  4

3 5 7 8 74:26 97:3  98:2  98:2  99:1 (α) 99:1 (α) 99:1 (α) 99:1 (α) 9173 88 ^([d]) 81  5  6

3 8 60:40 95:5  99:1 (α) 99:1 (α) quant. ^([e]) 83 ^([f])  7  8

8 8 98:2  75:25 99:1 (α) 94:6 (α) 84 (R = H)^([g]) 86 (R = Ac)  9 10

8 8 97:3  98:2  99:1 (α) 99:1 (α) 77 (R = H) 72 (R = butyl) 11

8 99:1  99:1 (α) 97 12

8 81:19 95:5 (α) 81 13

8 83:17 99:1 (α) 86 14

8 99:1  99:1 (α) 90 15 16

3 8 50:50 90:10 91:9 (β) 96:4 (α) 77 87^([d,h]) 17 18

3    8^([i]) 40:60  6:94 99:1 (β) 95:5 (β) 90 71^([i,j]) 19

8 93:7  99:1 (α) 87^([h,k]) 20

8 94:6  98:2 83% 21

8 96:4  99:1 88% 22

7 96:4  99:1 83% 23

7 95:5  96:4 86% 24

8 97:3  99:1 66% 25

8 99:1  99:1 84% 26

8 99:1  87:13 60%^([j]) 27

8 96:4  99:1 37% 28

8 98:2  99:1 92% 29

8 99:1  99:1 55% 30

8 95:5  99:1 81% 31

7 77:23 96:1 92% 32

7 87:13 94:6 98% 33

7 95:5  95:5 90% 34

7 100:0  91:9 78% 35

8 n.d. 99:1 55% ^([a])unless stated otherwise, all reactions wereperformed on 0.1-0.2 mmol scale by adding Bu₃SnH (1.1 equiv.) over ≈5min to a solution of the substrate and the respective catalyst in CH₂Cl₂(0.2M) under Ar; ^([b])using 3 or 5 or 7 (5 mol %), or 8 (1.25 mol %);^([c]) ratio is the crude product, as determined by ¹H NMR; α refers tothe compound bearing the tin residue proximal to the protic site,whereas β refers to the compound bearing the tin residue distal to theprotic site; ^([d]) ≧1 mmol scale; ^([e]) conversion (¹H NMR); ^([f])2.1 mmol scale; ^([g])small amounts of the corresponding ketone werealso found; ^([h])using 1.0 eq. of Bu₃SnH; ^([i])the substrate was addedover 1.5 h; ^([j])the yield refers to the pure major isomer after flashchromatography; ^([k])0.6 mmol scale; n.d. = not determined

Thus, by the present invention, the inventors have shown that simpleruthenium catalysts, most notably complexes [Cp*Ru(MeCN)₃]PF₆,[Cp*Ru(cod)Cl], [Cp*RuCl₂]_(n), or [(Cp*RuCl)₄] (Cp*=η⁵-C₅Me₅), some ofwhich are commercially available, allow the fundamental and largelyunchallenged rule of suprafacial delivery of hydrogen and tin to thesame π-face of a given starting material (cis-addition mode) to bebroken for alkynes as the substrates. Moreover, the present invention issuperior to the trans-hydrostannation of alkynes based on the use ofcatalytic or stoichiometric amounts of strong Lewis acids such as ZrCl₄,HfCl₄ or fluorinated borane derivatives, notably with regard to thefunctional group tolerance as well as the user-friendliness. Thesearching of libraries of matching candidates of alkyne, rutheniumcatalyst and tin hydride provides the simple means of finding the bestsystem for a given transition Ru-catalyzed conversion. This procedure issimple and can be performed rapidly by standard laboratory techniquesor, alternatively, with modern instruments which are customary incombinatorial catalysis. The resulting trans-hydrostannation opens apractical new gateway to Z-configured alkenyltin derivatives which couldpreviously only be made by indirect routes or by radical processes,which however often lead to mixtures of isomers or to differentregioisomers. The inventors expect this stereo-complementary methodologyto add another dimension to the uniquely prolific field of organotinchemistry. The inventive alkenyltin derivatives can be used for furthersynthesis of, for example, drug compounds or drug candidates, naturalproducts, fine chemicals, agrochemicals, polymers, liquid crystals,fragrances, flavors, cosmetic ingredients, sun protective agents.Furthermore, they can be used for the preparation of compound librariesby combinatorial or parallel synthesis.

The invention is further illustrated by the general method fortrans-hydrostannation as shown in Example 1 and further exemplified inthe subsequent Examples 2 to 42 for various products of thetrans-hydrostannation of alkynes.

EXAMPLE 1 (Z)-Tributyl(dec-5-en-5-yl)stannane

Tributyltin hydride (0.99 mL, 3.68 mmol, 1.05 equiv) was added dropwiseunder Argon over 6 min to a stirred solution of and 5-decyne (0.63 mL,3.5 mmol, 1.0 equiv) and [Cp*Ru(CH₃CN)₃]PF₆ (88.2 mg, 0.175 mmol, 0.05equiv) in dry CH₂Cl₂ (17.5 mL) at ambient temperature. Once the additionwas complete, stirring was continued for another 15 min before thesolvent was evaporated. The residue was purified by filtration through ashort pad of silica using hexane as the eluent. Evaporation of theproduct-containing fractions afforded (Z)-tributyl(dec-5-en-5-yl)stannane as a colorless oil (1.42 g, 94%) (Z/E>99:1(NMR)). ¹H NMR (400 MHz, CDCl₃): δ=5.98 (tt, J=7.1, 1.2 Hz, 1H),2.25-2.05 (m, 2H), 2.03-1.91 (m, 2H), 1.59-1.39 (m, 6H), 1.39-1.22 (m,14H), 1.00-0.80 (m, 21H); ¹³C NMR (101 MHz, CDCl₃): δ=143.4, 140.8,40.6, 34.9, 33.1, 32.8, 29.4, 27.6, 22.7, 22.4, 14.3, 14.2, 13.8, 10.4;IR (v_(max)/cm⁻¹) 2955, 2922, 2872, 2854, 1463, 1377, 1071.

EXAMPLE 2 Diethyl 2-(tributylstannyl)fumarate

Prepared analogously as a pale yellow oil (63.8 mg, 69%) (Z/E>99:1(NMR)). ¹H NMR (400 MHz, CDCl₃): δ=6.82 (s, 1H), 4.22 (q, J=7.1 Hz, 2H),4.20 (q, J=7.2 Hz, 2H), 1.58-1.37 (m, 6H), 1.37-1.24 (m, 12H), 1.14-0.94(m, 6H), 0.88 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=172.5,167.4, 161.7, 134.8, 61.19, 61.15, 29.1, 27.4, 14.43, 14.36, 13.8, 12.1;IR (v_(max)/cm⁻¹) 2956, 2921, 2872, 2853, 1709, 1463, 1367, 1313, 1193,1036; ESI-MS calcd for C₂₀H₃₈O₄SnNa (M+Na⁺) 485.16836. found 485.16858.

EXAMPLE 3 (Z)-2-(Tributylstannyl)but-2-ene-1,4-diyl diacetate

Prepared analogously as a colorless oil (73.8 mg, 80%) (Z/E=99:1 (NMR));¹H NMR (400 MHz, CDCl₃): δ=6.39 (tt, J=6.9, 1.6 Hz, 1H), 4.74-4.63 (m,2H), 4.56-4.47 (m, 2H), 2.07 (s, 3H), 2.06 (s, 3H), 1.57-1.39 (m, 6H),1.38-1.25 (m, 6H), 1.03-0.93 (m, 6H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR(101 MHz, CDCl₃): δ=170.8, 170.6, 145.6, 135.6, 71.1, 65.7, 29.1, 27.4,21.10, 21.08, 13.8, 10.6; IR (v_(max)/cm⁻¹) 2956, 2925, 2872, 2853,1740, 1459, 1376, 1217, 1077, 1021; ESI-MS calcd for C₂₀H₃₈O₄SnNa(M+Na⁺) 485.16836. found 485.16855.

EXAMPLE 4 (Z)-Tributyl(1,12-dibromododec-6-en-6-yl)stannane

Prepared analogously as a colorless oil (49.1 mg, 80%). (Z/E=97:3(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=5.97 (tt, J=7.2, 1.2 Hz, 1H), 3.40(td, J=6.8, 3.3 Hz, 4H), 2.26-2.06 (m, 2H), 2.04-1.93 (m, 2H), 1.93-1.78(m, 4H), 1.57-1.37 (m, 12H), 1.37-1.25 (m, 8H), 0.99-0.80 (m, 15H); ¹³CNMR (101 MHz, CDCl₃): δ=143.6, 140.6, 40.6, 34.9, 34.1, 33.9, 33.0,32.9, 29.9, 29.6, 29.4, 28.2, 27.9, 27.6, 13.7, 10.5; IR (v_(max)/cm⁻¹)2955, 2924, 2870, 2853, 1459, 1264, 1071.

EXAMPLE 5 (Z)-3-(Tributylstannyl)hex-3-ene-1,6-diylbis(4-methylbenzene-sulfonate)

Prepared analogously as a colorless oil (69.6 mg, 98%) (Z/E=99:1 (NMR));¹H NMR (400 MHz, CDCl₃): δ=7.77 (dq, J=8.5, 2.1 Hz, 4H), 7.39-7.31 (m,4H), 5.85 (tt, J=7.1, 1.3 Hz, 1H), 3.95 (t, J=6.9 Hz, 2H), 3.88 (t,J=7.4 Hz, 2H), 2.52-2.38 (m, 8H), 2.32 (q, J=7.0 Hz, 2H), 1.45-1.31 (m,6H), 1.32-1.19 (m, 6H), 0.86 (t, J=7.3 Hz, 9H), 0.84-0.79 (m, 6H); ¹³CNMR (101 MHz, CDCl₃): δ=145.0, 144.9, 142.2, 137.8, 133.3, 133.2,130.01, 129.99, 128.1, 128.0, 69.9, 69.6, 39.3, 34.5, 29.2, 27.4, 21.8,13.8, 10.3; IR (v_(max)/cm⁻¹) 2955, 2924, 2871, 2853, 1598, 1463, 1360,1188, 1174, 1097; ESI-MS calcd for C₃₂H₅₀O₆S₂SnNa (M+Na⁺) 737.19623.found 737.19663.

EXAMPLE 6 (Z)-Tributyl(1,12-diazidododec-6-en-6-yl)stannane

Prepared analogously as a yellow oil (30.2 mg, 56%) (Z/E=98:2 (NMR)); ¹HNMR (400 MHz, CDCl₃) δ=5.97 (tt, J=7.1, 1.3 Hz, 1H), 3.31-3.22 (m, 4H),2.27-2.05 (m, 2H), 2.05-1.91 (m, 2H), 1.67-1.54 (m, 4H), 1.53-1.42 (m,6H), 1.42-1.36 (m, 4H), 1.36-1.25 (m, 10H), 0.99-0.80 (m, 15H); ¹³C NMR(101 MHz, CDCl₃) δ=143.6, 140.6, 51.64, 51.57, 40.6, 34.9, 30.2, 30.0,29.4, 29.0, 28.9, 27.6, 26.7, 26.4, 13.8, 10.4; IR (v_(max)/cm⁻¹) 2954,2925, 2870, 2854, 2090, 1457, 1347, 1256, 1072.

EXAMPLE 7 (Z)-9-(Tributylstannyl)octadec-9-ene-2,17-dione

Prepared analogously as a colorless oil (53.3 mg, 94%) (Z/E=99:1 (NMR));¹H NMR (400 MHz, CDCl₃) δ=5.94 (tt, J=7.1, 1.3 Hz, 1H), 2.40 (td, J=7.5,1.8 Hz, 4H), 2.18-2.03 (m, 2H), 2.12 (s, 6H), 1.99-1.91 (m, 2H),1.61-1.51 (m, 4H), 1.50-1.41 (m, 6H), 1.37-1.21 (m, 18H), 0.95-0.79 (m,15H); ¹³C NMR (101 MHz, CDCl₃) δ=209.4, 209.3, 143.5, 140.7, 44.0, 43.9,40.8, 35.1, 30.7, 30.3, 29.97, 29.95, 29.41, 29.39, 29.36, 29.25, 29.1,27.6, 24.1, 24.0, 13.8, 10.4; IR (v_(max)/cm⁻¹) 2953, 2923, 2870, 2852,1717, 1458, 1417, 1357, 1161, 1071; ESI-MS calcd for C₃₀H₅₉O₂Sn (M+H⁺)571.35364. found 571.35409.

EXAMPLE 8 Ethyl (Z)-2-(tributylstannyl)but-2-enoate and Ethyl(Z)-3-(tributylstannyl)but-2-enoate

Prepared analogously as a mixture of regioisomers (α/β=1/1.5); colorlessoil (72.8 mg, 90%). The Z/E ratio (NMR) was found to be 99/1 for theβ-isomer and >99/1 for the α-isomer. The regioisomers can be separatedby flash chromatography (SiO₂) using hexanes/EtOAc (1/0→50/1→5/1) as theeluent.

Characteristic data of the β-Isomer: ¹H NMR (400 MHz, CDCl₃): δ=6.41 (q,J=1.7 Hz, 1H), 4.17 (q, J=7.1 Hz, 2H), 2.13 (d, J=1.7 Hz, 3H), 1.54-1.37(m, 6H), 1.36-1.23 (m, 9H), 1.07-0.91 (m, 6H), 0.88 (t, J=7.3 Hz, 9H);¹³C NMR (101 MHz, CDCl₃): δ=171.7, 167.9, 129.4, 60.2, 29.4, 27.6, 27.6,14.5, 13.9, 11.1; IR (v_(max)/cm⁻¹) 2955, 2920, 2871, 2852, 1701, 1600,1463, 1368, 1315, 1191, 1099, 1043; ESI-MS calcd for C₁₈H₃₆O₂SnNa(M+Na⁺) 427.16288. found 427.16337.

Characteristic data of the α-Isomer: ¹H NMR (400 MHz, CDCl₃): δ=7.46 (q,J=6.9 Hz, 1H), 4.15 (q, J=7.1 Hz, 2H), 1.91-1.85 (m, 3H), 1.56-1.42 (m,6H), 1.37-1.24 (m, 9H), 1.09-0.92 (m, 6H), 0.88 (t, J=7.3 Hz, 9H). ¹³CNMR (101 MHz, CDCl₃): δ=171.7, 152.3, 137.4, 60.5, 29.2, 27.4, 19.7,14.5, 13.8, 11.5.

EXAMPLE 9 (Z)-4-(Tributylstannyl)-4-(trimethylsilyl)but-3-en-1-ol

Prepared analogously as a mixture of regioisomers (α/β=96/4); colorlessoil (35.5 mg, 82%). The Z/E ratio (NMR) was found to be >99/1 for theα-isomer. Characteristic data of the α-Isomer: ¹H NMR (400 MHz, CDCl₃):δ=6.72 (t, J=6.6 Hz, 1H), 3.73 (t, J=6.6 Hz, 2H), 2.42 (q, J=6.6 Hz,2H), 1.59-1.38 (m, 6H), 1.38-1.25 (m, 7H), 1.04-0.92 (m, 6H), 0.89 (t,J=7.3 Hz, 9H), 0.05 (s, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=150.8, 148.0,62.3, 42.5, 29.4, 27.6, 13.8, 11.5, −0.1; IR (v_(max)/cm⁻¹) 3310, 2954,2923, 2871, 2854, 1571, 1463, 1376, 1245, 1046; ESI-MS calcd forC₁₉H₄₃OSiSn (M+H⁺) 435.21045. found 435.21003.

EXAMPLE 10 (Z)-4-(Tributylstannyl)-4-(trimethylsilyl)but-3-en-1-yl4-methoxybenzoate

Prepared analogously as a mixture of regioisomers (α/β=96/4); colorlessoil (111.7 mg, 98%); The Z/E ratio (NMR) was found to be >99/1 for theα-isomer. Characteristic data of the α-Isomer: ¹H NMR (400 MHz, CDCl₃)δ=8.05-7.95 (m, 2H), 6.95-6.88 (m, 2H), 6.78 (t, J=6.4 Hz, 1H), 4.37 (t,J=6.7 Hz, 2H), 3.86 (s, 3H), 2.65-2.52 (m, 2H), 1.57-1.38 (m, 6H),1.38-1.25 (m, 6H), 1.06-0.92 (m, 6H), 0.88 (t, J=7.3 Hz, 9H), 0.06 (s,9H); ¹³C NMR (101 MHz, CDCl₃) δ=166.4, 163.5, 150.3, 147.4, 131.7,123.0, 113.7, 63.9, 55.6, 38.5, 29.4, 27.5, 13.8, 11.4, −0.1; IR(v_(max)/cm⁻¹) 2954, 2926, 2871, 2853, 1715, 1607, 1511, 1459, 1273,1254, 1166, 1099, 1033.

EXAMPLE 11(Z)-(5-Chloro-5-(tributylstannyl)pent-4-en-1-yl)triethylsilane

Prepared analogously as a colorless oil (α/β>99:1) (47.6 mg, 94%)(Z/E>99:1 (NMR)); ¹H NMR (400 MHz, CDCl₃) δ=6.65 (t, J=6.6 Hz, 1H), 3.55(t, J=6.7 Hz, 2H), 2.36-2.23 (m, 2H), 1.96-1.85 (m, 2H), 1.57-1.39 (m,6H), 1.39-1.25 (m, 6H), 1.02-0.79 (m, 24H), 0.56 (q, J=7.9 Hz, 6H); ¹³CNMR (101 MHz, CDCl₃) δ=155.3, 141.6, 44.7, 36.9, 32.8, 29.4, 27.6, 13.8,11.6, 7.7, 3.9; IR (v_(max)/cm⁻¹) 2953, 2927, 2872, 2854, 1570, 1458,1376, 1235, 1071, 1003.

EXAMPLE 12 Methyl 5-(tri butylstannyl)hex-5-enoate

A solution containing methyl hex-5-ynoate (26 μL, 0.20 mmol, 1.0 equiv)and tributyltin hydride (0.22 mmol, 59 μL, 1.1 equiv) in CH₂Cl₂ (0.5 mL)was added dropwise over 12 min to a stirred solution of[Cp*Ru(CH₃CN)₃]PF₆ (5.0 mg, 10 μmol, 0.05 equiv) in CH₂Cl₂ (0.5 mL)under argon. Once the addition was complete, the mixture was stirred foranother 15 min before all volatile materials were evaporated. Theresidue was passed through a short plug of silica, eluting withhexanes/EtOAc (20:1) to give the title compound as a mixture ofregioisomers (terminal:internal=3:97) as a colorless oil (60.5 mg, 73%).Data of the major isomer: ¹H NMR (400 MHz, CDCl₃) δ=5.67 (dt, J=2.8, 1.5Hz, 1H), 5.14 (dt, J=2.3, 1.0 Hz, 1H), 3.66 (s, 3H), 2.37-2.20 (m, 4H),1.77-1.66 (m, 2H), 1.58-1.38 (m, 6H), 1.36-1.25 (m, 6H), 1.00-0.78 (m,15H); ¹³C NMR (101 MHz, CDCl₃) δ=174.1, 154.4, 125.9, 51.6, 40.6, 33.6,29.3, 27.5, 24.7, 13.8, 9.7; IR (v_(max)/cm⁻¹) 2955, 2925, 2872, 2852,1742, 1457, 1436, 1376, 1245, 1222, 1193, 1170, 1072.

EXAMPLE 13 (Z)-3-(Tributylstannyl)pent-3-en-2-ol

Tributyltin hydride (1.1 mmol, 0.30 mL, 1.1 equiv) was added dropwiseover 5 min to a stirred solution of [Cp*RuCl₂]_(n) (n≧2) (preparedaccording to: N. Oshima et al., Chem. Lett. 1984, 1161) (15.4 mg, 0.025mmol, 0.025 equiv) and 3-pentyn-2-ol (93 μL, 1.0 mmol, 1.0 equiv) inanhydrous CH₂Cl₂ (5.0 mL, 0.2 M) under argon. The resulting mixture wasstirred for 15 min before all volatile materials were evaporated. Theresidue was loaded on top of a flash column packed with SiO₂ and theproduct eluted with hexane/EtOAc (50/1→30/1) to give the title compoundas a pale yellow oil (329 mg, 88%, α/β isomer=98/2). The Z/E ratio wasfound to be >99/1 for the α-isomer. Characteristic data of the α-Isomer:¹H NMR (400 MHz, CDCl₃): δ=6.27 (qd, J=6.7, 1.2 Hz, 1H), 4.35 (qd,J=6.3, 3.1 Hz, 1H), 1.76-1.69 (m, 3H), 1.60-1.40 (m, 6H), 1.39-1.28 (m,7H), 1.21 (d, J=6.3 Hz, 3H), 1.07-0.92 (m, 6H), 0.89 (t, J=7.3 Hz, 9H);¹³C NMR (101 MHz, CDCl₃): δ=150.5, 133.6, 75.8, 29.4, 27.5, 24.4, 19.3,13.8, 11.0; IR (v_(max)/cm⁻¹) 3345, 2955, 2922, 2871, 2853, 1621, 1456,1375, 1289, 1248, 1069.

EXAMPLE 14 (Z)-2-(Tributylstannyl)pent-2-en-1-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (670 mg, 83%) (α/β=95/5) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.21 (tt, J=7.1, 1.4, J_(Sn—H)=122.9Hz, 1H), 4.25-4.08 (m, 2H), 2.10-1.98 (m, 2H), 1.59-1.39 (m, 6H),1.38-1.25 (m, 6H), 1.20 (t, J=5.9 Hz, 1H), 1.06-0.92 (m, 9H), 0.89 (t,J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=143.6, 142.6, 70.6, 29.4,27.9, 27.5, 14.6, 13.8, 10.4; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−52.3 ppm;IR (film, cm⁻¹): {tilde over (v)}=3316, 2956, 2923, 2871, 2851, 1622,1459, 1418, 1376, 1291, 1148, 1080, 1000; ESI-MS calcd for C₁₇H₃₅OSn(M−H⁻) 375.17147. found 375.17155.

EXAMPLE 15 (Z)-3-(Tributylstannyl)hex-3-en-2-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (65.5 mg, 84%) (α/β=98/2) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.15 (td, J=7.2, 1.1, J_(Sn—H)=125.7Hz, 1H), 4.34 (qdd, J=6.4, 3.4, 1.0 Hz, 1H), 2.09-1.94 (m, 2H),1.59-1.39 (m, 6H), 1.38-1.26 (m, 7H), 1.22 (d, J=6.3 Hz, 3H), 1.09-0.92(m, 9H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=148.4,141.2, 75.7, 29.4, 27.6, 27.5, 24.4, 14.6, 13.8, 11.2; ¹¹⁹Sn NMR (112MHz, CDCl₃): δ=−53.8 ppm; IR (film, cm⁻¹): {tilde over (v)}=3354, 2957,2923, 2871, 2853, 1619, 1458, 1376, 1287, 1247, 1149, 1115, 1070, 1005;ESI-MS calcd for C₁₈H₃₇OSn (M−H⁻) 389.18712. found 389.18728.

EXAMPLE 16 (Z)-3-(Tributylstannyl)hex-3-en-2-yl acetate

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (73.8 mg, 86%) (α/β=75:25) (Z/E=94:6 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.18 (td, J=7.2, 1.0, J_(Sn—H)=122.3Hz, 1H), 5.49-5.28 (m, 1H), 2.08-1.94 (m, 2H), 2.00 (s, 3H), 1.59-1.38(m, 6H), 1.38-1.27 (m, 6H), 1.25 (d, J=6.4 Hz, 3H), 1.05-0.85 (m, 18H);¹³C NMR (101 MHz, CDCl₃): δ=170.2, 151.1, 143.5, 78.6, 29.3, 27.54,27.50, 22.1, 21.7, 14.4, 13.8, 11.1; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−52.4ppm; IR (film, cm⁻¹): {tilde over (v)}=2957, 2926, 2871, 2854, 1737,1457, 1368, 1235, 1126, 1070, 1041, 1012; ESI-MS calcd for C₂₀H₄₀O₂SnNa(M+Na⁺) 455.19418. found 455.19459.

EXAMPLE 17 (2Z,7Z)-3-(Tributylstannyl)trideca-2,7-dien-4-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (69.5 mg, 72%) (α/β=98:2) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.25 (qd, J=6.6, 1.1, J_(Sn—H)=125.5Hz, 1H), 5.44-5.30 (m, 2H), 4.13 (td, J=6.7, 3.1 Hz, 1H), 2.16-1.95 (m,4H), 1.74 (d, J=6.5 Hz, 3H), 1.60-1.42 (m, 8H), 1.41 (d, J=3.2 Hz, 1H),1.39-1.23 (m, 12H), 1.08-0.93 (m, 6H), 0.92-0.84 (m, 12H); ¹³C NMR (101MHz, CDCl₃): δ=149.3, 134.9, 130.7, 129.2, 80.0, 37.8, 31.7, 29.6, 29.4,27.6, 27.4, 24.0, 22.8, 19.4, 14.2, 13.8, 11.1; ¹¹⁹Sn NMR (112 MHz,CDCl₃): δ=−55.6 ppm; IR (film, cm⁻¹): {tilde over (v)}=3466, 3004, 2955,2922, 2871, 2854, 1620, 1457, 1376, 1290, 1070, 1003; ESI-MS calcd forC₂₅H₄₉OSn (M−H⁻) 485.28102. found 485.28128.

EXAMPLE 18 (Z)-3-(Tributylstannyl)octa-2,7-dien-4-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (31.9 mg, 77%) (α/β=97:3) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.25 (qd, J=6.7, 1.1, J_(Sn—H)=125.0Hz, 1H), 5.83 (ddt, J=16.9, 10.2, 6.6 Hz, 1H), 5.02 (dq, J=17.1, 1.7 Hz,1H), 4.96 (ddt, J=10.2, 2.3, 1.3 Hz, 1H), 4.24-4.02 (m, 1H), 2.19-1.96(m, 2H), 1.74 (d, J=6.6 Hz, 3H), 1.66-1.42 (m, 8H), 1.41 (d, J=3.1 Hz,1H), 1.39-1.22 (m, 6H), 1.09-0.69 (m, 6H), 0.89 (t, J=7.3 Hz, 9H); ¹³CNMR (101 MHz, CDCl₃): δ=149.3, 138.7, 135.0, 114.8, 79.9, 36.9, 30.4,29.4, 27.6, 19.4, 13.8, 11.1; IR (film, cm⁻¹): {tilde over (v)}=3429,2956, 2922, 2871, 2853, 1641, 1620, 1456, 1376, 1260, 1071, 1046, 1016;ESI-MS calcd for C₂₀H₄₀OSnNa (M+Na⁺) 439.19926. found 439.19957.

EXAMPLE 19 (Z)-1-(1-(Tributylstannyl)prop-1-en-1-yl)cyclohexan-1-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (82.9 mg, 97%) (α/β=99:1) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.24 (q, J=6.7, J_(Sn—H)=137.8 Hz,1H), 1.74 (d, J=6.6 Hz, 3H), 1.69-1.53 (m, 6H), 1.53-1.38 (m, 9H),1.38-1.27 (m, 6H), 1.26 (s, 1H), 1.22-1.07 (m, 1H), 1.06-0.86 (m, 6H),0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=155.3, 130.3, 75.7,38.2, 29.4, 27.6, 25.7, 22.4, 19.3, 13.9, 12.4; ¹¹⁹Sn NMR (112 MHz,CDCl₃): δ=−55.7 ppm; IR (film, cm⁻¹): {tilde over (v)}=3449, 2953, 2923,2870, 2852, 1448, 1375, 1340, 1293, 1253, 1149, 1071; ESI-MS calcd forC₂₁H₄₂OSnNa (M+Na⁺) 453.21492. found 453.21520.

EXAMPLE 20 (Z)-3-(Tributylstannyl)pent-3-en-1-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (61.0 mg, 81%) (α/β=81:19) (Z/E=95:5 for the major isomer(NMR)); Data of the major isomer: ¹H NMR (400 MHz, CDCl₃): δ=6.20 (qt,J=6.6, 1.3, J_(Sn—H)=129.6 Hz, 1H), 3.53 (q, J=6.1 Hz, 2H), 2.53-2.34(m, 2H), 1.74 (dt, J=6.6, 0.9 Hz, 3H), 1.60-1.37 (m, 7H), 1.37-1.25 (m,6H), 1.03-0.84 (m, 6H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz,CDCl₃): δ=140.7, 138.6, 61.8, 43.6, 29.3, 27.5, 20.2, 13.8, 10.3; ¹¹⁹SnNMR (112 MHz, CDCl₃): δ=−52.6 ppm; IR (film, cm⁻¹): {tilde over(v)}=3319, 2955, 2922, 2871, 2852, 1620, 1462, 1418, 1376, 1291, 1181,1040; ESI-MS calcd for C₁₇H₃₅OSn (M−H⁻) 375.17147. found 375.17149.

EXAMPLE 21 (Z)-4-(Tributylstannyl)hex-4-en-1-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (66.7 mg, 86%) (α/β=83:17) (Z/E=99:1 for the major isomer(NMR)); Data of the major isomer: ¹H NMR (400 MHz, CDCl₃): δ=6.12 (qt,J=6.6, 1.3, J_(Sn—H)=132.7 Hz, 1H), 3.68-3.58 (m, 2H), 2.24 (ddt, J=8.7,6.3, 1.2 Hz, 2H), 1.70 (dt, J=6.6, 1.0 Hz, 3H), 1.66-1.38 (m, 8H),1.38-1.23 (m, 7H), 1.02-0.83 (m, 6H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR(101 MHz, CDCl₃): δ=144.3, 135.0, 62.8, 37.1, 33.6, 29.4, 27.6, 20.0,13.8, 10.3; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−53.0 ppm; IR (film, cm⁻¹):{tilde over (v)}=3318, 2955, 2923, 2871, 2852, 1456, 1376, 1291, 1180,1071, 1052, 1002; ESI-MS calcd for C₁₈H₃₇OSn (M−H⁻) 389.18712. found389.18720.

EXAMPLE 22(Z)-4-Methyl-N-(3-(tributylstannyl)hex-3-en-2-yl)benzenesulfonamide

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (48.7 mg, 90%) (α/β=99:1) (Z/E=99:1 (NMR)); ¹H NMR (400MHz, CDCl₃): δ=7.74-7.66 (m, 2H), 7.30-7.22 (m, 2H), 5.93 (td, J=7.2,1.0, J_(Sn—H)=120.7 Hz, 1H), 4.30 (d, J=6.3 Hz, 1H), 4.04-3.81 (m, 1H),2.41 (s, 3H), 1.94-1.79 (m, 2H), 1.53-1.32 (m, 6H), 1.37-1.22 (m, 6H),1.14 (d, J=6.7 Hz, 3H), 0.95-0.72 (m, 18H); ¹³C NMR (101 MHz, CDCl₃):δ=144.4, 143.2, 142.6, 138.2, 129.6, 127.5, 58.5, 29.3, 27.7, 27.5,23.9, 21.6, 14.3, 13.8, 11.0; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−52.9 ppm;IR (film, cm⁻¹): {tilde over (v)}=3268, 2956, 2924, 2871, 2853, 1456,1417, 1374, 1325, 1160, 1094, 1071; ESI-MS calcd for C₂₅H₄₅NO₂SSnNa(M+Na⁺) 566.20845. found 566.20883.

EXAMPLE 23 (Z)-2-(Tributylstannyl)hex-2-enoic acid

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst andlimiting the amount of Bu₃SnH to exactly 1 equivalent relative to thesubstrate; colorless oil (389 mg, 87%) (α/β=90:10) (Z/E=96:4 (NMR)); ¹HNMR (500 MHz, CDCl₃): δ=7.50 (t, J=7.3, J_(Sn—H)=103 Hz, 1H), 2.17 (q,J=7.4 Hz, 2H), 1.56-1.41 (m, 8H), 1.37-1.27 (m, 6H), 1.09-0.85 (m, 18H);¹³C NMR (126 MHz, CDCl₃): δ=177.5, 160.2, 135.8, 36.3, 29.2, 27.4, 22.5,14.0, 13.8, 11.5; ¹¹⁹Sn NMR (186 MHz, CDCl₃): δ=−45.7 ppm; IR (film,cm⁻¹): {tilde over (v)}=3042, 2956, 2922, 2871, 2853, 2621, 1662, 1600,1462, 1404, 1377, 1272, 1073; ESI-MS calcd for C₁₈H₃₅O₂Sn (M−H⁻)403.16638. found 403.16671.

EXAMPLE 24 (Z)-4-(Tributylstannyl)hex-4-enoic acid

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst andlimiting the amount of Bu₃SnH to exactly 1 equivalent relative to thesubstrate; colorless oil (211 mg, 87%) (α/β=93:7) (Z/E=99:1 (NMR)). Dataof the major isomer: ¹H NMR (500 MHz, CDCl₃): δ=6.14 (qt, J=6.6, 1.4,J_(Sn—H)=129.8 Hz, 1H), 2.56-2.40 (m, 2H), 2.40-2.28 (m, 2H), 1.69 (dt,J=6.5, 1.0 Hz, 3H), 1.57-1.40 (m, 6H), 1.38-1.26 (m, 6H), 1.01-0.86 (m,6H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (126 MHz, CDCl₃): δ=179.3, 142.3,135.8, 35.3, 35.2, 29.4, 27.5, 20.1, 13.8, 10.2; ¹¹⁹Sn NMR (186 MHz,CDCl₃): δ=−51.5 ppm; IR (film, cm⁻¹): {tilde over (v)}=3025, 2956, 2921,2872, 2853, 1708, 1455, 1416, 1376, 1291, 1210, 1071, 1021; ESI-MS calcdfor C₁₈H₃₅O₂Sn (M−H⁻) 403.16639. found 403.16678. Note: this product isprone to proto-destannation (ca. 10% after 24 h, NMR).

EXAMPLE 25 (Z)-3-Methyl-4-(tributylstannyl)non-4-en-2-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (74.3 mg, 83%) (α/β=94/6) (Z/E=98:2 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.07 (td, J=7.1, 1.1, J_(Sn—H)=138.1Hz, 1H), 3.67-3.54 (m, 1H), 2.38-2.19 (m, 1H), 2.02 (qd, J=7.2, 2.5 Hz,2H), 1.55-1.40 (m, 7H), 1.39-1.24 (m, 10H), 1.15 (d, J=6.3 Hz, 3H), 1.03(d, J=6.8 Hz, 3H), 0.98-0.81 (m, 9H), 0.89 (t, J=7.2 Hz, 9H); ¹³C NMR(101 MHz, CDCl₃): δ=147.0, 141.1, 69.7, 49.6, 35.1, 32.7, 29.4, 27.6,22.8, 21.2, 14.4, 14.3, 13.8, 11.0; ¹¹⁹Sn NMR (112 MHz, CDCl₃) δ=−52.2;IR (v_(max)/cm⁻¹): 3350, 2956, 2923, 2871, 2854, 1458, 1376, 1249, 1075,1019; ESI-MS calcd for C₂₂H₄₅OSn (M−H⁺) 445.24972. found 445.25022.

EXAMPLE 26 2-((Z)-1-(Tributylstannyl)hex-1-en-1-yl)cyclopentan-1-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (80.5 mg, 88%) (α/β=96/4) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.08 (td, J=7.1, 1.1, J_(Sn—H)=133.4Hz, 1H), 3.85 (q, J=7.1 Hz, 1H), 2.51-2.26 (m, 1H), 2.09-1.93 (m, 3H),1.86 (dtd, J=12.5, 8.3, 4.0 Hz, 1H), 1.79-1.67 (m, 1H), 1.58 (dddd,J=16.9, 12.3, 6.3, 3.3 Hz, 3H), 1.52-1.41 (m, 6H), 1.40-1.23 (m, 11H),1.01-0.79 (m, 9H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃):δ=145.0, 141.5, 77.7, 34.7, 33.2, 32.7, 31.0, 29.4, 27.6, 22.8, 21.0,14.2, 13.8, 11.1; ¹¹⁹Sn NMR (112 MHz, CDCl₃) δ=−53.5; IR (v_(max)/cm⁻¹):3343, 2955, 2923, 2871, 2854, 1463, 1376, 1339, 1292, 1150, 1071, 1001;ESI-MS calcd for C₂₃H₄₅OSn (M−H⁺) 457.24972. found 457.24996.

EXAMPLE 27 (Z)-3-Methyl-4-(tributylstannyl)hex-4-en-1-ol

Prepared analogously using [(Cp*RuCl₂)_(n)] (5 mol %) as the catalystand 1.15 equiv HSnBu₃; colorless oil (66.6 mg, 83%) (α/β=96/4) (Z/E=99:1for the major isomer (NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.13 (qd, J=6.6,0.9, _(Sn—H)=134.1 Hz, 1H), 3.60 (tdd, J=6.6, 5.4, 1.5 Hz, 2H),2.54-2.26 (m, 1H), 1.70 (d, J=6.5 Hz, 3H), 1.63-1.38 (m, 8H), 1.39-1.26(m, 7H), 1.03-0.84 (m, 6H), 0.98 (d, J=6.9 Hz, 3H), 0.89 (t, J=7.3 Hz,9H); ¹³C NMR (101 MHz, CDCl₃): δ=151.2, 133.1, 62.0, 41.8, 39.9, 29.4,27.6, 22.1, 19.7, 13.8, 11.1; ¹¹⁹Sn NMR (112 MHz, CDCl₃) δ=−55.1; IR(v_(max)/cm⁻¹): 3314, 2955, 2923, 2871, 2853, 1456, 1376, 1290, 1150,1068, 1051, 1011; ESI-MS calcd for C₁₉H₃₉OSn (M−H⁺) 403.20277. found403.20295.

EXAMPLE 28 (Z)-7-Hydroxy-8-(tributylstannyl)oxacyclododec-8-en-2-one

Prepared analogously using [(Cp*RuCl₂)_(n)] (5 mol %) as the catalystand 1.15 equiv HSnBu₃; colorless oil (44.8 mg, 86%) (α/β=95/5) (Z/E=96:4for the major isomer (NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.29 (ddd,J=10.3, 3.6, 0.9 Hz, 1H), 4.54-4.27 (m, 1H), 4.26-3.98 (m, 2H),2.51-2.38 (m, 2H), 2.21-2.05 (m, 2H), 1.99-1.87 (m, 1H), 1.87-1.76 (m,2H), 1.70 (tdd, J=12.7, 5.0, 2.7 Hz, 1H), 1.56-1.39 (m, 8H), 1.37-1.26(m, 8H), 1.15-1.03 (m, 1H), 1.02-0.86 (m, 6H), 0.89 (t, J=7.3 Hz, 9H);¹³C NMR (101 MHz, CDCl₃): δ=173.2, 144.9, 143.3, 80.1, 66.0, 35.5, 34.4,33.3, 29.4, 28.3, 27.6, 24.8, 22.1, 13.8, 11.3; ¹¹⁹Sn NMR (112 MHz,CDCl₃) δ=−59.8; IR (v_(max)/cm⁻¹): 3486, 2953, 2921, 2870, 2852, 1733,1455, 1376, 1293, 1248, 1156, 1072, 1016; ESI-MS calcd for C₂₃H₄₄O₃SnNa(M+Na⁺) 511.22039. found 511.22072.

EXAMPLE 29 Ethyl (Z)-4-hydroxy-3-(tributylstannyl)hept-2-enoate

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;the HSnBu₃ was added dropwise over 20 min; pale yellow oil (61.0 mg,66%) (α/β=97/3) (Z/E=99:1 for the major isomer (NMR)); ¹H NMR (400 MHz,CDCl₃): δ=6.61 (d, J=1.5, J_(Sn—H)=102.0 Hz, 1H), 4.44 (dtd, J=7.7, 4.1,1.7 Hz, 1H), 4.18 (qd, J=7.1, 2.9 Hz, 2H), 1.60 (d, J=4.0 Hz, 1H),1.58-1.35 (m, 10H), 1.35-1.23 (m, 9H), 1.10-0.80 (m, 9H), 0.88 (t, J=7.3Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=176.7, 168.1, 126.0, 77.0, 60.5,39.0, 29.4, 27.6, 19.2, 14.5, 14.1, 13.8, 11.8; ¹¹⁹Sn NMR (112 MHz,CDCl₃) δ=−52.2; IR (v_(max)/cm⁻¹): 3382, 2956, 2921, 2871, 2853, 1702,1463, 1368, 1304, 1188, 1132, 1044; ESI-MS calcd for C₂₁H₄₂O₃SnNa(M+Na⁺) 485.20474. found 485.20519.

EXAMPLE 30 (Z)-4-Phenyl-3-(tri butylstannyl)but-3-en-2-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;colorless oil (73.1 mg, 84%) (α/β=99/1) (Z/E=99:1 for the major isomer(NMR)); ¹H NMR (400 MHz, CDCl₃): δ=7.46 (s, J_(Sn—H)=122.6 Hz, 1H),7.36-7.24 (m, 3H), 7.24-7.18 (m, 2H), 4.69-4.50 (m, 1H), 1.63 (d, J=4.1Hz, 1H), 1.49-1.32 (m, 9H), 1.31-1.19 (m, 6H), 0.87 (t, J=7.2 Hz, 9H),0.84-0.68 (m, 6H); ¹³C NMR (101 MHz, CDCl₃): δ=154.3, 140.8, 138.5,128.2, 128.0, 127.1, 75.1, 29.2, 27.5, 24.4, 13.8, 11.6; ¹¹⁹Sn NMR (112MHz, CDCl₃) δ=−51.1; IR (v_(max)/cm⁻¹): 3350, 2955, 2921, 2870, 2852,1491, 1457, 1419, 1376, 1289, 1124, 1071; ESI-MS calcd for C₂₂H₃₇OSn(M−H⁺) 437.18712. found 437.18732.

EXAMPLE 31 (2Z,4E)-2-(Tributylstannyl)nona-2,4-dien-1-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;the HSnBu₃ was added as a solution in 0.5 mL CH₂Cl₂ over 2 h and theproduct was purified by column chromatography (Al₂O₃), pale yellow oil(54.4 mg, 60%) (α/β=99/1) (Z/E=87:13 for the major isomer (NMR))isolated as pure Z-isomer. ¹H NMR (400 MHz, CDCl₃): δ=6.78 (dq, J=10.4,1.2, J_(Sn—H)=116.6 Hz, 1H), 6.00 (ddt, J=15.0, 10.5, 1.5 Hz, 1H), 5.73(dt, J=14.5, 6.9 Hz, 1H), 4.34-4.18 (m, 2H), 2.15-2.07 (m, 2H),1.60-1.41 (m, 6H), 1.41-1.20 (m, 11H), 1.09-0.91 (m, 6H), 0.90 (t, J=7.1Hz, 3H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=146.2,140.3, 136.9, 131.1, 70.5, 32.5, 31.3, 29.3, 27.5, 22.3, 14.1, 13.8,10.5; ¹¹⁹Sn NMR (112 MHz, CDCl₃) δ=−50.2; IR (v_(max)/cm⁻¹): 3323, 2955,2922, 2871, 2853, 1463, 1376, 1291, 1071, 1001, 958; ESI-MS calcd forC₂₁H₄₁OSn (M−H⁺) 429.21842. found 429.21862.

EXAMPLE 32 (2E,4E)-Hexa-2,4-dien-1-yl(Z)-6-hydroxy-7-(tributylstannyl)dodec-7-enoate

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst;HSnBu₃ was added as a solution in 0.5 mL CH₂Cl₂ over 2 h; pale yellowoil (43.5 mg, 37%) (α/β=96/4) (Z/E=99:1 for the major isomer (NMR)). ¹HNMR (400 MHz, CDCl₃): δ=6.24 (dd, J=15.2, 10.4 Hz, 1H), 6.13 (td, J=7.2,1.0, J_(Sn—H)=128.7 Hz, 1H), 6.05 (ddd, J=15.0, 10.4, 1.7 Hz, 1H),5.81-5.68 (m, 1H), 5.61 (dt, J=14.5, 6.6 Hz, 1H), 4.56 (d, J=6.6 Hz,2H), 4.19-3.98 (m, 1H), 2.38-2.26 (m, 2H), 2.08-1.95 (m, 2H), 1.79-1.73(m, 3H), 1.68-1.59 (m, 2H), 1.56-1.41 (m, 6H), 1.42-1.22 (m, 15H),1.04-0.80 (m, 9H), 0.89 (t, J=7.2 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃):δ=173.6, 147.7, 141.2, 134.9, 131.4, 130.6, 123.9, 80.2, 63.0, 37.4,34.5, 34.1, 32.4, 29.4, 27.6, 25.7, 25.0, 22.7, 18.3, 14.2, 13.9, 11.2;¹¹⁹Sn NMR (112 MHz, CDCl₃) δ=−55.2; IR (v_(max)/cm⁻¹): 3502, 2954, 2923,2871, 2854, 1736, 1458, 1377, 1230, 1157, 1071, 987; ESI-MS calcd forC₃₀H₅₅O₃SnNa (M+Na⁺) 607.31429. found 607.31469.

EXAMPLE 33 (Z)-2-(1-(Tributylstannyl)dec-1-en-1-yl)-1H-indole

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %); the compound waspurified by column chromatography over Al₂O₃; orange oil (88.3 mg, 81%)(α/β=95/5) (Z/E=99:1 for the major isomer (NMR)); ¹H NMR (400 MHz,CDCl₃): δ=7.98-7.88 (bs, 1H), 7.53 (d, J=7.7 Hz, 1H), 7.29 (dq, J=8.0,1.0 Hz, 1H), 7.11 (ddd, J=8.1, 7.1, 1.3 Hz, 1H), 7.05 (ddd, J=8.2, 7.1,1.2 Hz, 1H), 6.57 (t, J=7.3, J_(Sn—H)=117.4 Hz, 1H), 6.20 (dd, J=2.2,0.9 Hz, 1H), 2.21 (q, J=7.4 Hz, 2H), 1.62-1.41 (m, 8H), 1.41-1.23 (m,16H), 1.15-0.95 (m, 6H), 0.94-0.85 (m, 12H); ¹³C NMR (101 MHz, CDCl₃):δ=144.1, 143.4, 136.0, 134.3, 129.4, 121.5, 120.1, 119.7, 110.4, 100.7,35.2, 32.0, 30.3, 29.8, 29.7, 29.5, 29.2, 27.5, 22.8, 14.3, 13.8, 11.6;¹¹⁹Sn NMR (112 MHz, CDCl₃) δ=−47.8; IR (v_(max)/cm⁻¹): 3417, 2955, 2922,2870, 2852, 1454, 1376, 1342, 1290, 1072, 1014; ESI-MS calcd forC₃₀H₅₀NSn (M−H⁺) 544.29700. found 544.29749.

EXAMPLE 34 (Z)-N-(3-(Tributylstannyl)pent-3-en-1-yl)acetamide

Prepared analogously using [(Cp*RuCl₂)_(n)] (5 mol %) as the catalystand 1.15 equiv HSnBu₃; colorless oil (81.8 mg, 98%) (α/β=87/13)(Z/E=94:6 for the major isomer (NMR)); ¹H NMR (400 MHz, CDCl₃): δ=6.16(dt, J=6.5, 1.3, _(Sn—H)=126.9 Hz, 1H), 5.42-5.28 (bs, 1H), 3.21 (td,J=6.8, 5.4 Hz, 2H), 2.44-2.25 (m, 2H), 1.95 (s, 3H), 1.73 (dt, J=6.5,1.0 Hz, 3H), 1.56-1.39 (m, 6H), 1.37-1.24 (m, 6H), 1.02-0.84 (m, 6H),0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=169.9, 141.7, 137.4,40.1, 39.2, 29.4, 27.5, 23.5, 20.1, 13.8, 10.2; ¹¹⁹Sn NMR (112 MHz,CDCl₃) δ=−52.5; IR (v_(max)/cm⁻¹): 3281, 3084, 2955, 2922, 2871, 2852,1649, 1556, 1456, 1375, 1293, 1206, 1071; ESI-MS calcd for C₁₉H₃₉NOSnNa(M+Na⁺) 440.19451. found 440.19479.

EXAMPLE 35(Z)-1,1,1-Trifluoro-N-(3-(tributylstannyl)pent-3-en-1-yl)methane-sulfonamide

Prepared analogously with (Cp*RuCl₂)_(n) in CH₂Cl₂, pale yellow oil (79mg, 78%, α only, Z/E=91:1 (NMR)). ¹H NMR (400 MHz, CDCl₃): δ=6.21 (qt,J=6.6, 1.2 Hz, 1H), 4.77 (s (br), NH), 3.25 (q, J=5.6, 2H), 2.46 (t,J=6.6, 2H) 1.75 (d, J=6.4, 3H), 1.52-1.43 (m, 6H), 1.37-1.27 (m, 6H),0.97-0.92 (m, 6H), 0.90 (t, J=7.2, 9H); ¹³C NMR (101 MHz, CDCl₃):δ=139.7, 139.6, 119.7 (q, J=320 Hz), 43.6, 40.6, 29.2, 27.3, 20.0, 13.6,10.0; ¹¹⁹Sn (112 MHz, CDCl₃): δ=−51.4; IR (film/cm⁻¹) {tilde over(v)}=3308, 2957, 2924, 2873, 2853, 1620, 1420, 1373, 1230, 1187, 1147,1065, 962, 875, 864, 845; ESI-MS calcd for C₁₈H₃₅F₃NO₂SSn (M−H)506.13674. found 506.13716.

EXAMPLE 36(Z)-2,2,2-Trifluoro-N-(3-(tributylstannyl)pent-3-en-1-yl)acetamide

Prepared analogously with (Cp*RuCl₂)_(n) in CH₂Cl₂; colorless oil (87mg, 90%, α:β=95:5, Z/E=95:5 for the major isomer (NMR)). ¹H NMR (400MHz, CDCl₃): δ=6.20 (q, J=6.5 Hz, 1H+NH), 3.32 (q, J=6.2, 2H), 2.43 (t,J=6.6, 2H) 1.75 (d, J=6.5, 3H), 1.51-1.42 (m, 6H), 1.36-1.27 (m, 6H),0.98-0.92 (m, 6H), 0.90 (t, J=7, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=156.8(q, J=36 Hz), 140.4, 138.6, 115.9 (q, J=288 Hz), 39.3, 39.1, 29.2, 27.3,19.9, 13.6, 10.0; ¹¹⁹Sn (112 MHz, CDCl₃): δ=−51.4; IR (film/cm⁻¹) {tildeover (v)}=3303, 3102, 2957, 2924, 2873, 2853, 1701, 1620, 1558, 1457,1376, 1340, 1293, 1204, 1161, 1072, 1022, 960, 875, 864, 831, 769, 724,688, 665; ESI-MS calcd for C₁₉H₃₆F₃NOSnNa (M+Na⁺) 494.16625. found494.16661.

EXAMPLE 37 tert-Butyl (Z)-(3-(tributylstannyl)pent-3-en-1-yl)carbamate

Prepared analogously with (Cp*RuCl₂)_(n) in CH₂Cl₂; pale yellow oil (88mg, 92%, α:β=77:23; Z/E=96:1 for the major isomer (NMR)). ¹H NMR (400MHz, CDCl₃): δ=6.15 (q, J=6.5 Hz), 4.43 (s (br), NH), 3.08 (m), 2.32 (t,J=6.5 Hz), 1.72 (d, J=6.5 Hz), 1.53-1.42 (m), 1.44 (s), 1.36-1.26 (m),0.95-0.85 (m); ¹³C NMR (101 MHz, CDCl₃): δ=155.8, 141.3, 137.2, 78.9,40.4, 35.1, 29.2, 28.4, 27.4, 20.0, 13.7, 10.0; ¹¹⁹Sn (112 MHz, CDCl₃):δ=−52.2; IR (film/cm⁻¹) {tilde over (v)}=3443, 3366, 2956, 2924, 2872,2853, 1706, 1620, 1502, 1456, 1390, 1376, 1365, 1340, 1248, 1071, 1021,998, 961, 872, 834, 778, 688, 666; ESI-MS calcd for C₂₂H₄₅NOSnNa (M+Na⁺)498.23638. found 498.23692.

EXAMPLE 38 (Z)-3-(Tributylstannyl)hexadec-2-en-14-yn-4-ol

Prepared analogously using [(Cp*RuCl)₄] (1.25 mol %) as the catalyst and1.05 equiv. of Bu₃SnH; purification by flash chromatography(hexane/EtOAc, 100/1→20/1) allowed minor by-products to be removed andgave the title compound as a colorless oil (57.7 mg, 55%). ¹H NMR (400MHz, CDCl₃): δ=6.23 (qd, J=6.6, 1.0, J_(Sn—H)=126.0 Hz, 1H), 4.20-3.98(m, 1H), 2.11 (tq, J=7.3, 2.5 Hz, 2H), 1.78 (t, J=2.5 Hz, 3H), 1.73 (d,J=6.5 Hz, 3H), 1.57-1.40 (m, 9H), 1.40-1.18 (m, 20H), 1.06-0.87 (m, 6H),0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=149.6, 134.8, 80.5,79.6, 75.4, 37.9, 29.8, 29.7, 29.4, 29.34, 29.27, 29.1, 27.6, 26.1,19.4, 18.9, 13.8, 11.1, 3.6; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−55.2 ppm; IR(film, cm⁻¹): {tilde over (v)}=3468, 2954, 2922, 2853, 1462, 1375, 1290,1148, 1070, 1046, 1004; ESI-MS calcd for C₂₈H₅₄OSnNa (M+Na⁺) 549.30881.found 549.30917.

EXAMPLE 39 4-(Trimethylsilyl)but-3-yn-1-yl4-(tributylstannyl)pent-4-enoate

Prepared according to the procedure detailed in Example 1 using[Cp*Ru(MeCN)₃]PF₆ as the catalyst and exactly 1.0 equiv. of Bu₃SnH;colorless oil (isomer ratio for stannylation at the terminal versus thesilylated triple bond=93:7) (98.2 mg, 96%); data of major isomer: ¹H NMR(400 MHz, CDCl₃): δ=5.70 (dt, J=2.3, 1.6, J_(Sn—H)=133.2 Hz, 1H), 5.15(dt, J=2.3, 1.2, J_(Sn—H)=62.4 Hz, 1H), 4.16 (t, J=7.1 Hz, 2H),2.64-2.46 (m, 4H), 2.46-2.34 (m, 2H), 1.59-1.40 (m, 6H), 1.38-1.25 (m,6H), 1.00-0.82 (m, 15H), 0.15 (s, 9H); ¹³C NMR (101 MHz, CDCl₃):δ=173.0, 153.1, 125.6, 102.4, 86.6, 62.3, 35.8, 34.1, 29.2, 27.5, 20.5,13.8, 9.7, 0.2; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−44.0 ppm; IR (film,cm⁻¹): {tilde over (v)}=2956, 2925, 2872, 2853, 2181, 1741, 1457, 1419,1377, 1337, 1248, 1162, 1071, 1026; ESI-MS calcd for C₂₄H₄₆O₂SiSnNa(M+Na⁺) 537.21806. found 537.21852.

EXAMPLE 40 Pent-3-yn-1-yl 4-(tributylstannyl)pent-4-enoate

Prepared according to the procedure detailed in Example 1 using[Cp*Ru(MeCN)₃]PF₆ as the catalyst and exactly 1.0 equiv. of Bu₃SnH;colorless oil (isomer ratio for stannylation at the terminal versus theinternal triple bond=76:24) (80.6 mg, 89%); ¹H NMR (400 MHz, CDCl₃):δ=5.70 (dq, J=3.5, 1.7, J_(Sn—H)=135.0 Hz, 1H), 5.15 (dq, J=2.0, 1.0,J_(Sn—H)=62.6 Hz, 1H), 4.13 (t, J=7.0 Hz, 2H), 2.65-2.50 (m, 2H),2.50-2.34 (m, 4H), 1.77 (t, J=2.5 Hz, 3H), 1.63-1.38 (m, 6H), 1.37-1.23(m, 6H), 1.01-0.82 (m, 6H), 0.89 (t, J=7.3 Hz, 9H); ¹³C NMR (101 MHz,CDCl₃): δ=173.1, 153.2, 125.5, 77.4, 74.9, 62.9, 35.8, 34.0, 29.2, 27.5,19.4, 13.8, 9.7, 3.6; ¹¹⁹Sn NMR (112 MHz, CDCl₃): δ=−44.0 ppm; IR (film,cm⁻¹): {tilde over (v)}=2955, 2922, 2871, 2852, 1739, 1457, 1419, 1377,1340, 1245, 1165, 1072, 1002; ESI-MS calcd for C₂₂H₄₀O₂SnNa (M+Na⁺)479.19418. found 479.19459.

EXAMPLE 41(Z)-Tributyl(1-(4-(trifluoromethyl)phenyl)prop-1-en-1-yl)stannane

Prepared according to the procedure detailed in Example 1 using[Cp*Ru(MeCN)₃]PF₆ as the catalyst; colorless oil (88.4 mg, 93%)(α/β=65:35) (Z/E=99:1, α-isomer (NMR)); Data of major α-isomer: ¹H NMR(500 MHz, CD₂Cl₂): δ=7.53-7.48 (m, 2H), 7.12 (d, J=7.9 Hz, 2H), 6.32 (q,J=6.7 Hz, 1H), 1.91 (d, J=6.7 Hz, 3H), 1.51-1.40 (m, 6H), 1.32-1.24 (m,6H), 1.05-0.89 (m, 6H), 0.86 (t, J=7.3 Hz, 9H); ¹³C NMR (126 MHz,CD₂Cl₂, resolved signals): δ=152.7, 146.2, 140.3, 127.7, 127.3, 125.4,125.4, 125.4, 125.3, 29.6, 27.9, 20.8, 14.0, 11.4; ¹¹⁹Sn NMR (186 MHz,CD₂Cl₂): δ=−48.1 ppm; IR (film, cm⁻¹): {tilde over (v)}=2957,

EXAMPLE 42 (Z)-Trimethyl(2-(tributylstannyl)oct-2-en-1-yl)silane

Prepared according to the procedure detailed in Example 1 using[Cp*Ru(MeCN)₃]PF₆ (5 mol %) as the catalyst; colorless oil (38.7 mg,82%) (α/β=79/21) (Z/E=95:5 for the major isomer (NMR)). ¹H NMR (400 MHz,CDCl₃): δ=5.84 (tt, J=7.2, 1.2, J_(Sn—H)=139.7 Hz, 1H), 1.95 (q, J=7.0Hz, 2H), 1.66 (s, 2H), 1.58-1.40 (m, 6H), 1.38-1.22 (m, 12H), 0.98-0.80(m, 18H), −0.03 (s, 9H); ¹³C NMR (101 MHz, CDCl₃): δ=139.1, 138.6, 35.8,31.9, 30.6, 29.4, 29.0, 27.7, 22.9, 14.3, 13.8, 10.7, −1.2; ¹¹⁹Sn NMR(112 MHz, CDCl₃) δ=−53.6; IR (v_(max)/cm⁻¹): 2955, 2923, 2871, 2854,1463, 1377, 1246, 1149, 1071, 837; El-MS calcd for C₂₃H₅₀SiSn (M+Na⁺)474.27031. found 474.27003.

The invention claimed is:
 1. A process for highly stereoselectivetrans-hydrostannation of alkynes comprising the steps of reacting analkyne of the formula (I)

with a tin hydride of the formula X¹X²X³SnH in the presence of aruthenium catalyst to yield an alkene of the formula (II):

Wherein: R¹ and R² are the same or different and are each selected from:I. straight chain or branched chain aliphatic hydrocarbons, or cyclicaliphatic hydrocarbons, said aliphatic hydrocarbons optionally havingheteroatoms and/or aromatic hydrocarbons and/or heteroaromatichydrocarbons in the chain and/or having one or more substituentsselected from C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatichydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, or heteroatoms, or II. aromatic hydrocarbonshaving 5 to 20 carbon atoms or heteroaromatic hydrocarbons having 1 to20 carbon atoms, said aromatic or heteroaromatic hydrocarbons eachoptionally having one or more substituents selected from C₁-C₂₀-alkyl,C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic hydrocarbon, C₅ to C₂₀heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, heteroatoms, or one of R¹ and R² is selectedfrom hydrogen, halogen, or —SiR*R**R***, wherein R*, R**, R*** can bethe same or different and shave the meaning as given under I. and II.,and the other of R¹ and R² has the meaning as given under I, and II, orR¹ and R² together form an aliphatic hydrocarbon chain having 6 to 30carbon atoms, optionally having heteroatoms and/or aromatic hydrocarbonsin the chain and/or optionally having one or more substituents selectedfrom C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatichydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, said aliphatic hydrocarbon chain optionallybeing substituted by one or more substituents selected fromheterosubstituents, straight chain, branched chain, cyclic aliphatic C₁to C₂₀ hydrocarbons, C₆ to C₂₀ aromatic hydrocarbon, C₅ toheteroaromatic hydrocarbon, aryl-(C₁-C₆)-alkyl, orheteroaryl-(C₁-C₆)-alkyl or heteroatoms; wherein the substituents X¹, X²and X³ in the formula X¹X²X³SnH are the same or different and are eachselected from hydrogen, straight chain, branched chain or cyclicaliphatic hydrocarbons, aromatic hydrocarbons, or two of X¹ X² and X³together form an aliphatic hydrocarbon chain having 2 to 20 carbonatoms, said hydrocarbon group optionally having heteroatoms in the chainand/or optionally having one or more substituents selected fromC₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic hydrocarbon,C₁ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, having identical or different alkyl groupswith 2 to 12 carbon atoms, halogen or heteroatoms wherein at least twoof X¹, X² and X³ are not hydrogen; and wherein the catalyst is acyclopentadienyl-coordinated ruthenium complex containing the followingsubstructure:

wherein R_(cp1) to R_(cp5) are the same or different and are eachselected from hydrogen or from straight chain, branched chain or cyclicaliphatic hydrocarbons, optionally having heteroatoms and/or aromatichydrocarbons in the chain and/or optionally having one or moresubstituents selected from C₁-C₂₀-alkyl, heterocycloalkyl, C₆ to C₂₀aromatic hydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon oraryl-(C₁-C₆)-alkyl, heteroaryl-(C₁-C₆)-alkyl or heteroatoms and whereinfurther ligands are coordinated to the central atom Ruthenium. 2.Process for highly stereoselective trans-hydrostannation of alkynesaccording to claim 1 wherein R¹ and R² are the same or different and areeach selected from straight chain or branched chain aliphatichydrocarbons having 1 to 20 carbon atoms optionally having heteroatomsand/or aromatic hydrocarbons in the chain or aromatic hydrocarbonshaving 5 to 20 carbon atoms, optionally having one or more substituentsselected from C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatichydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, or heteroatoms, or R¹ and R² together form analiphatic hydrocarbon chain structure having 8 to 20 carbon atoms,optionally having heteroatoms and/or aromatic hydrocarbons in the chainand/or optionally having one or more substituents selected fromC₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatic hydrocarbon,C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, said chain structure optionally beingsubstituted by one or more substituents selected fromheterosubstituents, straight chain, branched chain, cyclic aliphatic C₁to C₂₀ hydrocarbons, C₆ to C₂₀ aromatic hydrocarbon, C₅ to C₂₀heteroaromatic hydrocarbon, aryl-(C₁-C₆)-alkyl, orheteroaryl-(C₁-C₆)-alkyl, or one of R¹ and R² is selected from hydrogen,halogen, —SiR*R**R***, wherein R*, R**, R*** are the same or differentand are each selected from straight chain or branched chain aliphatichydrocarbons having 1 to 20 carbon atoms optionally having heteroatomsand/or aromatic hydrocarbons in the chain or aromatic hydrocarbonshaving 5 to 20 carbon atoms, optionally having one or more substituentsselected from C₁-C₂₀-alkyl, C₅-C₈-heterocycloalkyl or C₆ to C₂₀ aromatichydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon or aryl-(C₁-C₆)-alkyl,heteroaryl-(C₁-C₆)-alkyl, or heteroatoms.
 3. Process for highlystereoselective trans-hydrostannation of alkynes according to claim 1wherein the substituents X¹, X² and X³ in the formula X¹X²X³ SnH are thesame or different and are each selected from straight chain, branchedchain or cyclic C₁ to C₁₀ aliphatic hydrocarbons each optionally beingsubstituted by methyl, ethyl, propyl, butyl or isomers thereof, or oneor more fluorine atoms.
 4. Process for highly stereoselectivetrans-hydrostannation of alkynes according to claim 1 wherein thecatalyst used in the inventive process is a cyclopentadienyl-coordinatedruthenium complex comprising the following substructure:

wherein R_(cp1) to R_(cp5) are the same or different and are eachselected from hydrogen or from straight chain, branched chain or cyclicaliphatic hydrocarbons, optionally having heteroatoms and/or aromatichydrocarbons in the chain and/or optionally having one or moresubstituents selected from C₁-C₂₀-alkyl, heterocycloalkyl, C₆ to C₂₀aromatic hydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon oraryl-(C₁-C₆)-alkyl, heteroaryl-(C₁-C₆)-alkyl or heteroatoms and whereinfurther ligands coordinated to the central atom ruthenium.
 5. Processfor highly stereoselective trans-hydrostannation of alkynes accordingclaim 1 wherein the catalyst is [Cp*RuL₃]X wherein Cp*=η⁵-C₅R_(5cp) witheach R_(cp) being H or CH₃, and L being the same or differentligand/substituent and being selected from electron-donatingligands/substituents, or wherein the catalyst is a complex of theformula [Cp*RuY_(n)] wherein Cp*=η⁵-C₅R_(5cp) with each R_(cp) being Hor CH₃, and Y is an anionic ligand being selected from hydrogen, halogenand n=2, 3, or a dimer or oligomer of the formula [Cp*RuY₂]_(n) whereinCp*=η⁵-C₅R₅ with R being H or CH₃ and Y is an anionic ligand and beingselected from hydrogen, halogen and n≧2.
 6. Process for highlystereoselective trans-hydroboration of internal alkynes according toclaim 1 wherein the following complex is used as catalyst:

wherein the substituent R is selected from H or Me and X^(⊖) is ananionic counter ion.
 7. Process for highly stereoselectivetrans-hydrostannation of alkynes according to claim 5 wherein theanionic counterion is selected from PF₆, SbF₆ ⁻, BF₄ ⁻, ClO₄ ⁻, F₃CCOO⁻,Tf₂N⁻, (Tf=trifluoromethanesulfonyl), TfO⁻, tosyl,[B[3,5-(CF₃)₂C₆H₃]₄]⁻, B(C₆F₅)₄ ⁻ or Al(OC(CF₃)₃)₄ ⁻.
 8. Process forhighly stereoselective trans-hydrostannation of alkynes according toclaim 1 wherein the catalyst is selected from the following complexes:

wherein the substituent X is selected from Cl, Br, I, and n is ≧2. 9.Process for highly stereoselective trans-hydrostannation ofunsymmetrical alkynes according to claim 1, in which the catalyst isselected depending on the alkyne in order to control the ratio ofregioisomers formed.
 10. A process comprising conducting ahydrostannation reaction in the presence of an organic tin compound anda catalyst, wherein the catalyst is a ruthenium catalyst comprising acyclopentadienyl-coordinated ruthenium complex comprising the followingsubstructure:

wherein R_(cp1) to R_(cp5) are the same or different and are eachselected from hydrogen or from straight chain, branched chain or cyclicaliphatic hydrocarbons, optionally having heteroatoms and/or aromatichydrocarbons in the chain and/or optionally having one or moresubstituents selected from C₁-C₂₀-alkyl, heterocycloalkyl, C₆ to C₂₀aromatic hydrocarbon, C₅ to C₂₀ heteroaromatic hydrocarbon oraryl-(C₁-C₆)-alkyl, heteroaryl-(C₁-C₆)-alkyl or heteroatoms and whereinfurther ligands L are coordinated to the central atom ruthenium.